01966nas a2200241 4500008004100000020001800041022001400059245007800073210006900151260009500220300001200315490000600327520112400333653003001457653002501487653001901512653002201531100001601553700001801569700001601587700001301603856010801616 2005 eng d a90-6764-442-0 a1573-419600aDensity functional response approach for electric properties of molecules0 aDensity functional response approach for electric properties of  aCorinth, GreecebVsp BV-C/o Brill Acad Publ, Po Box 9000, 2300 Pa Leiden, NetherlandscOCT a142-1510 v33 a

We review in this paper an implementation of the response approach to the Kohn-Sham (KS) density functional theory (DFT) for obtaining the linear and non-linear electric response properties of molecules using Gaussian type orbital basis centered on atoms. We have made a formulation in which the response of the electron density through the solution of the coupled perturbed Kohn-Sham (CPKS) equations has to be obtained only once, instead of iteratively as in the case of completely analytic procedure. Our method is based on a numerical finite-field solution of derivative KS operator, followed by analytic solution of CPKS equation. Further, using the response of the electron density, the dipole moment, polarizability and first-hyperpolarizability of the molecules are evaluated. The method is particularly useful for large systems. We tested our method using HF, BH, H2O and CO as test molecules, for which, high quality ab initio results are available. Further, our study of possible incorporation of non-dynamical electron correlation by studying BH and HF at several internuclear distances is discussed.

10aDensity functional theory10amolecular properties10apolarizability10aResponse approach1 aPal, Sourav1 aSophy, K., B.1 aMaroulis, G1 aSimos, T uhttps://library.ncl.res.in/content/density-functional-response-approach-electric-properties-molecules-002480nas a2200229 4500008004100000022001400041245009600055210006900151260010600220300001600326490000700342520157700349653002701926653003001953653003001983653002102013653003202034100001702066700002402083700001602107856012702123 2011 eng d a0360-319900aAb initio and periodic DFT investigation of hydrogen storage on light metal-decorated MOF-50 aAb initio and periodic DFT investigation of hydrogen storage on  aTHE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, ENGLANDbPERGAMON-ELSEVIER SCIENCE LTDcAUG a10816-108270 v363 a

The effect of light metal (M = Li, Be, Mg, and Al) decoration on the stability of metal organic framework MOF-5 and its hydrogen adsorption is investigated by ab initio and periodic density functional theory (DFT) calculations by employing models of the form BDC:M-2:nH(2) and MOF-5:M-2:nH(2), where BDC stands for the benzenedicarboxylate organic linker and MOF-5 represents the primitive unit cell. The suitability of the periodic DFT method employing the GGA-PBE functional is tested against MP2/6-311 + G* and MP2/cc-pVTZ molecular calculations. A correlation between the charge transfer and interaction energies is revealed. The metal-MOF-5 interactions are analyzed using the frontier molecular orbital approach. Difference charge density plots show that H-2 molecules get polarized due to the charge generated on the metal atom adsorbed over the BDC linker, resulting in electrostatic guest-host interactions. Our solid state results show that amongst the four metal atoms, Mg and Be decoration does not stabilize the MOF-5 to any significant extent. Li and Al decoration strengthened the H-2-MOE-5 interactions relative to the pure MOF-5 exhibited by the enhanced binding energies. The hydrogen binding energies for the Li- and Al-decorated MOF-5 were found to be sensible for allowing reversible hydrogen storage at ambient temperatures. A high hydrogen uptake of 4.3 wt.% and 3.9 wt.% is also predicted for the Li- and Al-decorated MOF-5, respectively. Copyright (C) 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

10aab initio calculations10aDensity functional theory10aHydrogen binding energies10aHydrogen storage10aMetal-Pi-Arene interactions1 aDixit, Mudit1 aMaark, Tuhina, Adit1 aPal, Sourav uhttps://library.ncl.res.in/content/ab-initio-and-periodic-dft-investigation-hydrogen-storage-light-metal-decorated-mof-5-001859nas a2200229 4500008004100000022001400041245010400055210006900159260007300228300001200301490000800313520098400321653001801305653004001323653003001363653002201393653002501415100002401440700002601464700001601490856012301506 2012 eng d a0920-586100aFirst principle investigation on the thermal stability of a golden fullerene: a case study of Au-320 aFirst principle investigation on the thermal stability of a gold aPO BOX 211, 1000 AE AMSTERDAM, NETHERLANDSbELSEVIER SCIENCE BVcDEC a106-1090 v1983 a

Structural and electronic properties of Au-32 cluster are analyzed using relativistic density functional theory (DFT) based methods. Further, DFT based molecular dynamical (MD) simulations are performed on Au-32 golden fullerene with an aim of understanding its thermal stability at various working temperatures. Various conformations being populated at different temperatures of a cluster are analyzed. The study shows that the ground state icosahedral conformation is stable only up to 300 K and structure remains in a hollow conformation only up to 400 K. This clearly explains the reasons for failure by experimentalists in trapping the unique fullerene conformation in spite of the theoretical predictions of it being a very stable one. The above MD study also indicates that the bare fullerene Au-32 cluster (without any stabilizing ligands) can be used for potential catalytic applications only around room temperatures. (C) 2012 Elsevier B. V. All rights reserved.

10aAu-32 cluster10aBorn-Oppenheimer molecular dynamics10aDensity functional theory10aGolden fullerenes10aRelativistic effects1 aDe, Himadri, Sekhar1 aKrishnamurty, Sailaja1 aPal, Sourav uhttps://library.ncl.res.in/content/first-principle-investigation-thermal-stability-golden-fullerene-case-study-au-32-001657nas a2200217 4500008004100000022001400041245010500055210006900160260007100229300001200300490000600312520083400318653001401152653003001166653003101196653003001227100002101257700001601278700001701294856012801311 2013 eng d a2155-543500aMetal or nonmetal cooperation with a phenyl group: route to catalysis? a computational investigation0 aMetal or nonmetal cooperation with a phenyl group route to catal a1155 16TH ST, NW, WASHINGTON, DC 20036 USAbAMER CHEMICAL SOCcMAY a920-9270 v33 a

Full quantum mechanical calculations demonstrate that cooperativity in the form of the activation of the M-C bond (M: transition metal or boron, C: the ipso carbon of the coordinated phenyl group) can lead to effective catalysis pathways. Calculations show that the presence of an aromatic bidentate ligand attached to a transition metal, or even a main group element, such as boron, can lead to effective catalysts for,a, range of important reactions, such as the dehydrogenation of ammonia borane and formic acid and the activation of the N-H, bond in aromatic amities. Moreover, it is shown that the design of tridentate pincer complexes with the aromatic group at a terminal end can lead to effective M-C cooperativity. As such, the current work introduces a new concept in cooperativity and bond activation chemistry.

10acatalysis10aDensity functional theory10ametal-ligand cooperativity10asmall molecule activation1 aGhatak, Kamalika1 aMane, Manoj1 aVanka, Kumar uhttps://library.ncl.res.in/content/metal-or-nonmetal-cooperation-phenyl-group-route-catalysis-computational-investigation-002356nas a2200265 4500008004100000022001400041245016800055210006900223260010600292300001400398490000700412520129400419653003001713653002001743653001701763653002301780653004101803100002001844700001701864700002401881700001601905700001601921700002201937856013101959 2014 eng d a0360-319900aPhotoelectrochemical splitting of water with nanocrystalline Zn1-xMnxO thin films: first-principle DFT computations supporting the systematic experimental endeavor0 aPhotoelectrochemical splitting of water with nanocrystalline Zn1 aTHE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, ENGLANDbPERGAMON-ELSEVIER SCIENCE LTDcMAR a3637-36480 v393 a

Photoelectrochemical splitting of water with nanocrystalline Zn1-xMnxO thin films was investigated. ZnO thin films with 1, 3, 5 and 7% at. Mn incorporation were synthesized by sol gel method and characterized by X-Ray Diffraction (XRD) analysis, Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM), X-ray Photoelectron spectroscopy (XPS), High Resolution Transmission Electron Microscopy (HR-TEM) and UV-Vis spectroscopy. Mn incorporation coupled with variation in sintering temperature led to significant microstructural changes, which tentatively influenced the magnitude of optical absorption and charge carrier mobility, thereby impacting the performance of such systems towards photoelectrochemical splitting of water. Electronic structure computations based on first principle density functional theory (DFT) revealed electronic states of Mn being responsible for the marginally recorded red shift in bandgap energy. Photoelectrochemical measurements using thin films of 1% at. Mn:ZnO sintered at 600 degrees C yielded 3 times enhanced photocurrent at zero bias due to improved optical absorption. Plausible explanations for the effect have also been offered. Copyright (C) 2014, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

10aDensity functional theory10aHydrogen energy10aMn doped ZnO10aOptical properties10aPhotoelectrochemical water splitting1 aSharma, Vidhika1 aDixit, Mudit1 aSatsangi, Vibha, R.1 aDass, Sahab1 aPal, Sourav1 aShrivastav, Rohit uhttps://library.ncl.res.in/content/photoelectrochemical-splitting-water-nanocrystalline-zn1-xmnxo-thin-films-first-principle-001749nas a2200217 4500008004100000022001400041245011700055210006900172260006700241300001200308490000700320520093400327653001201261653001301273653003001286653002201316653003201338100002401370700001701394856012001411 2015 eng d a0192-865100aCan substituted allenes be highly efficient leaving groups in catalytic processes? a computational investigation0 aCan substituted allenes be highly efficient leaving groups in ca a111 RIVER ST, HOBOKEN 07030-5774, NJ USAbWILEY-BLACKWELLcAPR a795-8040 v363 a

There is considerable interest presently in the chemistry of allenes. The current computational investigation looks into the possibility of using allenes and their derivatives as leaving groups. As it is well known, leaving groups are significant in catalytic processes for generating the active site. A full quantum mechanical study using density functional theory shows that allenes and their derivatives can function as excellent leaving groups. Indeed, the calculations show that they can be several orders of magnitude more effective than existing ligands for this purpose. The modification of second generation Grubbs' catalysts with these ligands suggests that the allene ligand cases that would be most effective are those having electron withdrawing groups, especially those that have the potential for supramolecular interactions between the substituent groups in the free state. (c) 2015 Wiley Periodicals, Inc.

10aallenes10acarbones10aDensity functional theory10aolefin metathesis10asupramolecular interactions1 aKuriakose, Nishamol1 aVanka, Kumar uhttps://library.ncl.res.in/content/can-substituted-allenes-be-highly-efficient-leaving-groups-catalytic-processes-001762nas a2200277 4500008004100000022001400041245006700055210006700122260008100189300001100270490000600281520085000287653003001137653001901167653001501186653001201201653001101213100002301224700002301247700002401270700002301294700001801317700002401335700002601359856009901385 2015 eng d a2053-159100aEnhanced electron field emission from NiCo2O4 nanosheet arrays0 aEnhanced electron field emission from NiCo2O4 nanosheet arrays aTEMPLE CIRCUS, TEMPLE WAY, BRISTOL BS1 6BE, ENGLANDbIOP PUBLISHING LTDcSEP a0950110 v23 a

Electron emission properties of electrodeposited spinel NiCo2O4 nanosheet arrays grown on Ni foam have been studied. The work function of NiCo2O4 was calculated by density functional theory using the plane-wave basis set and used to estimate the field enhancement factor. The NiCo2O4 nanosheet arrays exhibited a low turn-on field of 1.86 V mu m(-1) at 1 mu A cm(-2) and current density of 686 mu A cm(-2) at 3.2 V mu m(-1), with field enhancement factor beta = 1460 and good field emission current stability. The field emission properties of the NiCo2O4 nanosheet arrays showed enhanced performance compared to chemically prepared NiCo2O4 nanosheets. Hence, the nanosheet arrays have great potential as robust high performance vertical structure electron emitters for future flat panel displays and vacuum electronic device applications.

10aDensity functional theory10afield emission10ananosheets10aNiCo2O410aspinel1 aNaik, Kusha, Kumar1 aKhare, Ruchita, T.1 aGelamo, Rogerio, V.1 aMore, Mahendra, A.1 aThapa, Ranjit1 aLate, Dattatray, J.1 aRout, Chandra, Sekhar uhttps://library.ncl.res.in/content/enhanced-electron-field-emission-nico2o4-nanosheet-arrays-102575nas a2200277 4500008004100000022001400041245018000055210006900235260011200304300001400416490000700430520146700437653001401904653001601918653003001934653003201964653003501996653001402031100002102045700002102066700002202087700002002109700001802129700001902147856013102166 2015 eng d a0019-452200aNovel 2,6-diformyl-4-methyl phenol based chemosensor for Zn-II ion by ratiometric displacement of Cd-II ion and its application for cell imaging on human melanoma cancer cells0 aNovel 26diformyl4methyl phenol based chemosensor for ZnII ion by a5-A, NEW PALI RD, PO BOX 91, NEAR HOTEL TAJ HARI MAHAL, JODHPUR, 342 003, INDIAbSCIENTIFIC PUBL-INDIAcNOV a1729-17450 v923 a

A new chelating ligand [4-methyl-2,6-bis-(pyridin-2-yl-hydrazonomethyl)-phenol] (1) was prepared by the condensation of 2-hydrazinylpyridine with 2,6-diformyl-p-cresol. Compound 1 exhibits weak fluorescence due to intramolecular photoinduced electron transfer (PET). The sensor (1) demonstrates Zn2+-specific emission enhancement due to ``PET off'' process through a 1 : 1 binding mode with the metal ion. The fluorescence quantum yield of the chemosensor 1 is only 0.020, and it increases more than 14-fold (0.280) in the presence of one equivalent of the zinc ion. Interestingly, the introduction of other metal ions causes the fluorescence intensity to remain either unchanged or weakened except for Cd2+. Ratiometric displacement of Cd2+ ion from the complex by Zn2+ ion supports the formation of more stable sensor-Zn2+ complex over the sensor-Cd2+ complex. The experimental findings have been correlated with theoretical results using B3LYP functional and 6-31G(d,p), LANL2DZ basis set for Cd2+ (2) and Zn2+ (3) complex, respectively, by Density Functional Theory (DFT) method. Moreover, the ability of probe 1 to sense Zn2+ within human melanoma cancer cells has been explored, and the Zn2+-probing process in living cells was reversible. [Mn-2(PHMP)(2)](ClO4)(2) (4) and [Ni-2(PHMP)(H2O)(5)](NO3)(3) (5) have been also synthesized and characterized crystallographically and spectroscopically to understand the ligating behavior of the ligand PHMP.

10aCd-II ion10aChemosensor10aDensity functional theory10ahuman melanoma cancer cells10aphotoinduced electron transfer10aZn-II ion1 aMitra, Debarshan1 aVenkatathari, N.1 aSabharwal, S., C.1 aGodbole, S., V.1 aTyagi, A., K.1 aDas, Sangbrita uhttps://library.ncl.res.in/content/novel-26-diformyl-4-methyl-phenol-based-chemosensor-zn-ii-ion-ratiometric-displacement-cd-101813nas a2200241 4500008004100000022001400041245009600055210006900151260006700220300001200287490000800299520092200307653003001229653002401259653002801283653001801311653002801329100001801357700001901375700002701394700002601421856012401447 2015 eng d a0020-760800aTheoretical insight of nitric oxide adsorption on neutral and charged Pd-n (n=1-5) clusters0 aTheoretical insight of nitric oxide adsorption on neutral and ch a111 RIVER ST, HOBOKEN 07030-5774, NJ USAbWILEY-BLACKWELLcJUL a837-8450 v1153 a

Density functional theory (DFT) calculations within the framework of generalized gradient approximation have been used to systematically investigate the adsorption of nitric oxide (NO) molecule on neutral, cationic, and anionic Pd-n (n=1-5) clusters. NO coordinate to one Pd atom of the cluster by the end-on mode, where the tilted end-on structure is more favorable due to the additional electron in the * orbital. On the contrary, in the neutral and cationic Pd-2 system, NO coordinates to the bridge site of cluster preferably by the side-on mode. Charge transfer between Pd clusters and NO molecule and the corresponding weakening of NO bond is an essential factor for the adsorption. The NO stretching frequency follow the order of cationic>neutral>anionic. Binding energy of NO on anionic clusters is found to be greater than those of neutral and cationic clusters. (c) 2015 Wiley Periodicals, Inc.

10aDensity functional theory10aelectronic property10ageometric configuration10aNO adsorption10asmall palladium cluster1 aBegum, Pakiza1 aGogoi, Pranjal1 aMishra, Bhupesh, Kumar1 aDeka, Ramesh, Chandra uhttps://library.ncl.res.in/content/theoretical-insight-nitric-oxide-adsorption-neutral-and-charged-pd-n-n1-5-clusters-103075nas a2200265 4500008004100000022001400041245008500055210006900140260009200209300001200301490000700313520211500320653001902435653002602454653003002480653002202510653002802532653003002560653001602590100001702606700002602623700001702649700002702666856011602693 2016 eng d a0892-702200aDFT based assay for tailor-made terpyridine ligand-metal complexation properties0 aDFT based assay for tailormade terpyridine ligandmetal complexat a4 PARK SQUARE, MILTON PARK, ABINGDON OX14 4RN, OXON, ENGLANDbTAYLOR & FRANCIS LTDcMAY a618-6270 v423 a

Electron-rich terpyridine ligand and its metal complexes have a potential to grow as responsive surfaces by adapting their physicochemical properties as a function of environment. The responsiveness is brought about by judicious molecular level designing that is currently hindered due to lack of information and control on terpyridine (TPy)-metal (M) interactions at single molecule level. So far there is no organised understanding on the binding of different metals with TPy ligand and ways to modulate it. Being a large conjugated [GRAPHICS] system, TPy has a large scope to be functionalised with electron exchanging groups to alter its electronic structure and consequently its binding with metal atoms. In first report of such a kind, using density functional theory (DFT), we demonstrate that convenient modulation of TPy-M binding is possible through functionalisation of TPy for [GRAPHICS] , Ru, Fe, Mo and Au. Electron donating groups viz., CH [GRAPHICS] , OCH [GRAPHICS] , C [GRAPHICS] H [GRAPHICS] , NH [GRAPHICS] and electron withdrawing groups viz., CF [GRAPHICS] , COOH, CN and NO [GRAPHICS] are considered for functionalisation of TPy ligand. Significantly, the present work focuses on the functionalisation at 4 and 4 [GRAPHICS] positions of TPy molecule. The role of such a functionalisation in influencing the ligands structure-property correlation is missing in the literature to the best of our knowledge. The present investigation quantifies that by pertinent functionalisation of TPy, TPy-M binding energies can be modified up to [GRAPHICS] 60kcal/mol. Our results reveal that functionalisation leads to a considerable charge redistribution within the TPy-M complex with carbon atoms in pyridine rings functioning as major electron sink/source with a corresponding red/blue shift of [GRAPHICS] stretching frequency. This modifies the red-ox, optical and other chemical properties of TPy-M complexes. In brief, the present report illustrates a way to design ligands such as TPy for diverse applications through tailor-made functionalisation using electronic structure methodology.

10aBinding energy10acharge redistribution10aDensity functional theory10afunctionalisation10aMetal organic complexes10ametal-ligand interactions10aterpyridine1 aJoshi, Krati1 aKrishnamurty, Sailaja1 aSingh, Iksha1 aSelvaraj, Kaliaperumal uhttps://library.ncl.res.in/content/dft-based-assay-tailor-made-terpyridine-ligand-metal-complexation-properties02442nas a2200277 4500008004100000022001400041245010600055210006900161260010600230300001200336490000800348520141600356653003001772653001701802653001401819653001601833653002201849100002401871700003001895700001701925700002901942700002101971700002001992700002402012856012802036 2016 eng d a0277-538700aPhotoluminescent tetrahedral d(10)-metal Schiff base complexes exhibiting highly ordered mesomorphism0 aPhotoluminescent tetrahedral d10metal Schiff base complexes exhi aTHE BOULEVARD, LANGFORD LANE, KIDLINGTON, OXFORD OX5 1GB, ENGLANDbPERGAMON-ELSEVIER SCIENCE LTDcFEB a150-1580 v1053 a

A series of four-coordinate d(10)-metal complexes of the type [ML2] {M = Zn, Cd, Hg; L = 4-nitro-2-((octadecylimino)methyl)phenol}, incorporating a new N-alkylated bidentate [N,O]-donor salicylaldimine Schiff base ligand, has been synthesized and characterized by elemental analyses, FT-IR, UV-Vis, H-1 NMR and FAB-mass spectroscopies. The ligand is non-mesomorphic and devoid of any photoluminescence. The zinc(II) and cadmium(II) complexes displayed highly ordered mesophases reminiscent of soft crystals. The phases have been characterized by polarizing optical microscopy (POM), differential scanning calorimetry (DSC) and powder X-ray diffraction (PXRD) studies. The complex of mercury(II) decomposed prior to melting. An orthogonal symmetry with a `herringbone' array for the zinc complex and a primitive triclinic symmetry (p(1)) for the cadmium complex, respectively, has been proposed. The complexes exhibited fluorescence at room temperature, both in the solution and in the solid state, with emission maxima in the blue region. Density functional theory (DFT) calculations carried out using the GAUSSIAN 09 program at the B3LYP level revealed a distorted tetrahedral geometry around the metal center in all the complexes. Natural bond orbital (NBO) analysis suggested appreciable charge transfer from the ligand to the metal center in the complexes. (C) 2015 Elsevier Ltd. All rights reserved.

10aDensity functional theory10aLuminescence10aMesophase10aSchiff base10aX-ray diffraction1 aChakraborty, Sutapa1 aPurkayastha, Debraj, Dhar1 aDas, Gobinda1 aBhattacharjee, Chira, R.1 aMondal, Paritosh1 aPrasad, Krishna1 aRao, D., S. Shankar uhttps://library.ncl.res.in/content/photoluminescent-tetrahedral-d10-metal-schiff-base-complexes-exhibiting-highly-ordered-102043nas a2200265 4500008004100000022001400041245014200055210006900197260000800266300001200274490000800286520106600294653002501360653002801385653003001413653001901443653003701462653002401499653002801523100002501551700001601576700002801592700003001620856012701650 2017 eng d a0026-924700aComputational survey of ligand properties on iron(III)-iron(II) redox potential: exploring natural attenuation of nitroaromatic compounds0 aComputational survey of ligand properties on ironIIIironII redox cAPR a655-6680 v1483 a

This study is a computational investigation of the ligand effect on the redox potential of iron redox couple aimed at screening these systems for novel applications. The influence of common and naturally available organic compounds with diverse ligand characteristics (nature of donor site, chelation, pre-organization, degree of back acceptance) on the redox potential of iron(III)-iron(II) redox couple has been theoretically calculated using an appropriate level of density functional theory (DFT). The DFT calculated redox potentials of iron complexes are explored to supplement, corroborate, and predict the experimental behavior of the studied systems towards environmental reduction of nitroaromatic compounds to corresponding anilines. The comparative avidity of iron complexes with cysteine derivatives for the reduction of nitroaromatic compounds has been theoretically explored and based on structure-activity relationship; new iron complexes with a range of reactivity and enhanced ability towards nitroaromatic reduction have been predicted.

10aCatechol derivatives10acomputational chemistry10aDensity functional theory10aIron complexes10aLigand effect on redox potential10aNatural attenuation10aNitroaromatic compounds1 aRizvi, Masood, Ahmad1 aMane, Manoj1 aKhuroo, Mohammad, Akbar1 aPeerzada, Ghulam, Mustafa uhttps://library.ncl.res.in/content/computational-survey-ligand-properties-ironiii-ironii-redox-potential-exploring-natural02139nas a2200253 4500008004100000022001400041245016900055210006900224260000800293300001400301490000600315520119100321653001901512653003001531653002001561653003201581653002801613100002801641700002501669700001801694700002101712700002401733856012801757 2017 eng d a2196-021600aNitrogen-doped graphene with a three-dimensional architecture assisted by carbon nitride tetrapods as an efficient metal-free electrocatalyst for hydrogen evolution0 aNitrogendoped graphene with a threedimensional architecture assi cOCT a2643-26520 v43 aCurrent polymer membrane-based electrolyzers use Pt as a cathode catalyst for efficient reduction of water. The high cost of Pt-based catalysts forces researchers to develop alternative electrocatalysts. Here, a simple strategy has been proposed to synthesize a metal-free electrocatalyst for the hydrogen evolution reaction (HER) by high-temperature annealing of graphene oxide-coated melamine foam. The prepared catalyst possesses both structural and functional advantages with its three-dimensional (3D) interconnected arms of carbon nitride (CNx) backbone wrapped with nitrogen-doped graphene (N-RGO) sheets (CNx@N-RGO). CNx@N-RGO faces only a 193 mV overpotential to achieve a current density of 10mAcm(-2), which is far superior to the previously reported Pt-free systems. Along with the high exchange current density 34.7 x 10(-6)A cm(-2) and low Tafel slope of 54 mV dec(-1), CNx@N-RGO follows a Volmer-Heyrovsky mechanism for the HER. DFT calculations show that the synergy between CNx and N-RGO facilitates good electrical coupling between the two moieties and provides optimal binding to H+ ions on the catalyst that, in turn, results in efficient reduction of hydrogen ions.10acarbon nitride10aDensity functional theory10aelectrocatalyst10ahydrogen evolution reaction10anitrogen doped graphene1 aGangadharan, Pranav, K.1 aUnni, SreeKuttan, M.1 aKumar, Nandha1 aGhosh, Prasenjit1 aKurungot, Sreekumar uhttps://library.ncl.res.in/content/nitrogen-doped-graphene-three-dimensional-architecture-assisted-carbon-nitride-tetrapods01982nas a2200241 4500008004100000022001400041245010800055210006900163260000800232300001400240490000600254520113500260653001801395653003001413653001301443653002501456653002301481653003301504653003401537100002501571700001701596856012701613 2018 eng d a2155-543500aB(C6F5)(3): catalyst or initiator? insights from computational studies into surrogate silicon chemistry0 aBC6F53 catalyst or initiator insights from computational studies cJUL a6163-61760 v83 a

One of the most promising recent developments in catalysis has been the use of the metal-free Lewis acid B(C6F5)(3) as a catalyst for a range of different chemical transformations. Perhaps the most impressive achievement in this regard is the recently accomplished in situ generation of SiH4 from surrogates (Simonneau and Oestreich, Nat. Chem., 2015,7, 816). However, what the current computational work, with density functional theory, reveals is that this process, in addition to being catalyzed by B(C6F5)(3), is also significantly dominated by a series of autocatalytic reactions. The results are further corroborated by the use of the energetic span model, which shows that the turnover frequency is higher for the newly proposed autocatalytic pathway in comparison to the conventional B(C6F5)(3)-catalyzed pathway. The current work therefore provides interesting new insights into surrogate silicon chemistry. But, more importantly, the current studies indicate that B(C6F5)(3) is likely to function more as an initiator rather than a pure catalyst in many metal-free transformations that have been reported to date.

10aautocatalysis10aDensity functional theory10aion-pair10aLewis acid catalysis10areaction mechanism10asurrogate silicone chemistry10atris(pentafluorophenyl)borane1 aBanerjee, Subhrashis1 aVanka, Kumar uhttps://library.ncl.res.in/content/bc6f53-catalyst-or-initiator-insights-computational-studies-surrogate-silicon-chemistry02277nas a2200217 4500008004100000022001400041245014600055210006900201260000900270300001200279490000800291520147800299653002201777653003001799653002301829653002501852100001801877700001501895700002201910856012701932 2018 eng d a0038-092X00aRevealing optoelectronic and transport properties of potential perovskites Cs2PdX6 (X = Cl, Br): A probe from density functional theory (DFT)0 aRevealing optoelectronic and transport properties of potential p cMAR  a336-3430 v1623 a

Metal-halide perovskites are rapidly emerging crystalline materials that are reasonably preferred as leading aspirant for applications in optoelectronic and thermoelectric devices. In this paper, we have thoroughly reviewed and performed calculations to reveal optoelectronic and transport properties for a potential newcomer, Cs2PdX6 (X = Cl, Br) termed as Cesium Palladium Halides (CPH). Outcome of present computations are compared with available results and a reasonable agreement is recorded. Energy band gap computations performed reveal indirect band gap of 2.29 eV for Cs2PdC16, which substantially reduces to 1.22 eV when `Cl' is replaced by `Br'. Optical absorption spectra investigations performed here, in the energy range from 3 to 5 eV confirms effective utilization of these compounds in solar cells and other optoelectronic applications. In addition, the transport properties computations performed using semi-classical Boltzmann theory, shows constant pattern of thereto power near ambient temperature range (200-500 K), which admits possible utilization of these compounds as low temperature thermoelectric materials. Performed ZT calculations demonstrates reasonably good thermoelectric performance for both materials, as there exist minor variation (0.1) in the values over wide temperature ranges i.e. from 100 to 800 K. Further, detailed analysis of transport properties predicts p-type semiconducting nature of the present series of materials.

10aAb-initio studies10aDensity functional theory10aOptical properties10aTransport properties1 aBhamu, K., C.1 aSoni, Amit1 aSahariya, Jagrati uhttps://library.ncl.res.in/content/revealing-optoelectronic-and-transport-properties-potential-perovskites-cs2pdx6-x-cl-br02331nas a2200253 4500008004100000022001300041245010500054210006900159260000800228300001400236490000700250520146200257653002401719653003001743653001901773653002701792100002201819700001701841700001801858700002001876700002401896700002601920856013101946 2018 eng d a1866689200aTuning of terahertz resonances of pyridyl benzamide derivatives by electronegative atom substitution0 aTuning of terahertz resonances of pyridyl benzamide derivatives  cJUL a636–6500 v393 a

N-(pyridin-2-yl) benzamide (Ph2AP)-based organic molecules with prominent terahertz (THz) signatures (less than 5 THz) have been synthesized. The THz resonances are tuned by substituting the most electronegative atom, fluorine, at ortho (2F-Ph2AP), meta (3F-Ph2AP), and para (4F-Ph2AP) positions in a Ph2AP molecule. Substitution of fluorine helps in varying the charge distribution of the atoms forming hydrogen bond and hence strength of the hydrogen bond is varied which helps in tuning the THz resonances. The tuning of lower THz resonances of 2F-Ph2AP, 3F-Ph2AP, and 4F-Ph2AP has been explained in terms of compliance constant (relaxed force constant). Four-molecule cluster simulations have been carried out using Gaussian09 software to calculate the compliance constant of the hydrogen bonds. Crystal structure simulations of the above molecules using CRYSTAL14 software have been carried out to understand the origin of THz resonances. It has been observed that THz resonances are shifted to higher frequencies with stronger hydrogen bonds. The study shows that 3F-Ph2AP and 4F-Ph2AP have higher hydrogen bond strength and hence the THz resonances originating due to stretching of intermolecular hydrogen bonds have been shifted to higher frequencies compared to 2F-Ph2AP. The methodology presented here will help in designing novel organic molecules by substituting various electronegative atoms in order to achieve prominent THz resonances.

10aCompliance constant10aDensity functional theory10aPh2AP molecule10aTerahertz spectroscopy1 aDash, Jyotirmayee1 aRay, Shaumik1 aDevi, Nirmala1 aBasutkar, Nitin1 aGonnade, Rajesh, G.1 aAmbade, Ashootosh, V. uhttps://library.ncl.res.in/content/tuning-terahertz-resonances-pyridyl-benzamide-derivatives-electronegative-atom-substitution02056nas a2200241 4500008004100000022001400041245014000055210006900195260000800264300001400272490000600286520118400292653003001476653002401506653001901530653002001549100002101569700002901590700001801619700002401637700002601661856012701687 2019 eng d a2168-048500aFacile production of mesoporous WO3-rGO hybrids for high-performance supercapacitor electrodes: an experimental and computational study0 aFacile production of mesoporous WO3rGO hybrids for highperforman cJAN a2350-23590 v73 a

This work explored a promising supercapacitor electrode material (WO3-rGO hybrids) synthesized via a simplistic one-pot hydrothermal synthesis route. Various analytical studies (X-ray diffraction study, Raman spectroscopy, field emission scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, Brunauer-Emmett-Teller analysis) were employed in furtherance to explore the structural, morphological, compositional, and surface areal properties of the prepared materials. The enhancement in electrochemical supercapacitive properties were evaluated from pure hexagonal phase WO3 to the various hybrids, depending on the concentration of GO introduced into it, using cyclic voltammetry, galvanostatic charge/discharge, and electrochemical impedance spectroscopy. The WG-80 composite revealed the high rise in capacitance value of 801.6 F/g overcoming the individual capacitance of rGO (71.11 F/g) and WO3 (94.22 F/g) at a current density of 4 A/g with good cycling stability (75.7%) over 5000 cycles. We have presented quantum capacitance from ab initio calculations and provided theoretical explanation from the orbital interactions.

10aDensity functional theory10aHydrothermal method10asupercapacitor10aWO3-rGO hybrids1 aSamal, Rutuparna1 aChakraborty, Brahmananda1 aSaxena, Manav1 aLate, Dattatray, J.1 aRout, Chandra, Sekhar uhttps://library.ncl.res.in/content/facile-production-mesoporous-wo3-rgo-hybrids-high-performance-supercapacitor-electrodes02068nas a2200301 4500008004100000022001100041245008100052210006900133260000800202300001200210490000800222520116200230653002101392653001701413653003001430653001901460653002401479653001801503100001401521700001501535700001901550700001701569700001701586700001801603700001901621700001701640856010901657 2019 eng d a22369700aVSe2-reduced graphene oxide as efficient cathode material for field emission0 aVSe2reduced graphene oxide as efficient cathode material for fie cMAY a384-3900 v1283 a

Field emission properties of pristine VSe2 and its hybrid with reduced graphene oxide (RGO) have been investigated in detail. Promising field emission performance were noted with lower values of turn-on and threshold fields of ∼1.3 V μm−1 and 2.12 V μm−1 respectively for the VSe2/RGO hybrid which is much more superior than that of pristine VSe2 emitter and other 2D materials. Density Functional Theory (DFT) simulations have also been performed to qualitatively support our experimental observations through demonstration of Density of States and computation of work function for pristine VSe2 and hybrid VSe2/RGO. The lowering of work function and appearance of additional states near Fermi level from carbon p orbital of RGO is responsible for superior field emission characteristics in hybrid VSe2/RGO compared to pristine VSe2 which supports our experimental observations. Our experimental data and theoretical insight from electronic structure simulations strongly infer that the synthesized hybrid VSe2/RGO has the potential to be tailored as efficient and high performance cathode material in field emission based devices.

10acathode material10aChalcogenide10aDensity functional theory10afield emission10aVanadium diselenide10aWork function1 aRatha, S.1 aBankar, P.1 aGangan, A., S.1 aMore, M., A.1 aLate, D., J.1 aBehra, J., N.1 aChkraborty, B.1 aRout, C., S. uhttps://library.ncl.res.in/content/vse2-reduced-graphene-oxide-efficient-cathode-material-field-emission02295nas a2200217 4500008004100000022001400041245016500055210006900220260000800289300001100297490000800308520148300316653003001799653002501829653002301854653001601877100001501893700001801908700002201926856012901948 2020 eng d a0925-838800aInvestigating effect of strain on electronic and optical properties of lead free double perovskite Cs2AgInCl6 solar cell compound: A first principle calculation0 aInvestigating effect of strain on electronic and optical propert cMAR a1527580 v8173 a

Despite serious problems associated with toxicity of lead, lead halide perovskite based solar cells have resulted with remarkable efficiency and hence gained much interest. To overcome this aspect, numerous solutions are attempted by researchers which include the development of new environmental friendly lead free double perovskite (DP) photovoltaic materials. Enlightening on the same line, we report first principle calculations on electronic and optical properties of Cs2AgInCl6 solar photovoltaic materials. Present opto-electronic computations for lead free DP compound, have been performed using the full potential linearized augmented plane wave method. In present investigations, we have adopted exchange and correlation potentials prescribed by Perdew et al. and the most accurate Tran-Blaha modified Becke-Johnson. Both exchange and correlation potential computations are performed with and without spin orbit coupling. Results obtained for electronic and optical properties are validated by systematic comparison with available experimental data. Reasonable reconciliation between investigated results and the available experimental data, endorse accuracy of present computations. To identify the effect of strain on energy gap and hence on the optical properties of Cs2AgInCl6 compound, computations of electronic and optical properties have also been performed under the different values of strain application. (C) 2019 Elsevier B.V. All rights reserved.

10aDensity functional theory10aElectronic Structure10aOptical properties10asolar cells1 aSoni, Amit1 aBhamu, K., C.1 aSahariya, Jagrati uhttps://library.ncl.res.in/content/investigating-effect-strain-electronic-and-optical-properties-lead-free-double-perovskite02701nas a2200265 4500008004100000022001400041245016000055210006900215260000800284300001100292490000800303520172400311653003002035653003202065653001702097653001902114653003702133100002202170700001902192700001702211700002502228700002602253700002702279856012902306 2020 eng d a0304-389400aUnravelling the distinct surface interactions of modified graphene nanostructures with methylene blue dye through experimental and computational approaches0 aUnravelling the distinct surface interactions of modified graphe cAPR a1217550 v3883 a

Nanoscopic modifications leading to multi-dimensional graphene structures are known to significantly influence their candidature for several applications including catalysis, energy storage, molecular sensing and most significantly adsorption and remediation of harmful materials such as dyes. The present work attempts to identify the key trajectories that connect the structural qualification with a chosen application, viz., the interactive forces in dye remediation. Various physico-chemically Modified Graphene Nanostructures (MGNs) such as 2 dimensional Graphite, Graphene Oxide (GO), reduced GO (rGO), holey rGO, and 3 dimensional GO hydrogel and Holey GO hydrogel are chosen and synthesised herein. These represent varieties of physicochemical features with respect to their dimensionality, surface features such as oxygen functionality, nanoscopic holes etc., that contribute to their characteristic overall surface interactions. Methylene Blue (MB), a popular industrial effluent posing major environmental concern is chosen to be a probe adsorbate in this case study. An exclusive real time in-situ UV visible spectral experiment provides the revealing reasons behind the outstanding performance of 2D GO sheets with an adsorption capacity of greater than 92 % even at high MB concentrations (>2000 ppm). A complex dependency of various factors such as surface oxygen, morphology, nanoporosity etc. on the unique overall interaction with an adsorbent such as MB by all these adsorbates is demonstrated using experimental and DFT based computational studies. Electrostatics and hydrogen bonding are understood to be the two dominant forces driving the MB adsorption on the best performing GO here.

10aDensity functional theory10aIn-situ UV-vis spectroscopy10aInteractions10aMethylene blue10aModified Graphene Nanostructures1 aManappadan, Zinoy1 aKumar, Shubham1 aJoshi, Krati1 aGovindaraja, Thillai1 aKrishnamurty, Sailaja1 aSelvaraj, Kaliaperumal uhttps://library.ncl.res.in/content/unravelling-distinct-surface-interactions-modified-graphene-nanostructures-methylene-blue01612nas a2200229 4500008004100000022001400041245009200055210006900147260000900216300001100225490000600236520083200242653003301074653002601107653003001133653004001163653002801203100002501231700001501256700001701271856009401288 2021 eng d a2296-264600aInsights into chemical reactions at the beginning of the universe: from HeH+ to H-3 (+)0 aInsights into chemical reactions at the beginning of the univers cJUN  a6797500 v93 aAt the dawn of the Universe, the ions of the light elements produced in the Big Bang nucleosynthesis recombined with each other. In our present study, we have tried to mimic the conditions in the early Universe to show how the recombination process would have led to the formation of the first ever formed diatomic species of the Universe: HeH+, as well as the subsequent processes that would have led to the formation of the simplest triatomic species: H-3 (+). We have also studied some special cases: higher positive charge with fewer number of hydrogen atoms in a dense atmosphere, and the formation of unusual and interesting linear, dicationic He chains beginning from light elements He and H in a positively charged atmosphere. For all the simulations, the ab initio nanoreactor (AINR) dynamics method has been employed.10aab initio molecular dynamics10aab initio nanoreactor10aDensity functional theory10aorigin of molecules in the universe10athe earliest lewis acid1 aDash, Soumya, Ranjan1 aDas, Tamal1 aVanka, Kumar uhttps://library.ncl.res.in/content/insights-chemical-reactions-beginning-universe-heh-h-302731nas a2200277 4500008004100000022001400041245015700055210006900212260000900281300001400290490000600304520175500310653001902065653003002084653003202114653001802146653001802164100001702182700001902199700001702218700002302235700002202258700003002280700001802310856012502328 2021 eng d a2574-096200aOne-dimensional multichannel g-C3N4.7 nanostructure realizing an efficient photocatalytic hydrogen evolution reaction and its theoretical investigations0 aOnedimensional multichannel gC3N47 nanostructure realizing an ef cAPR  a3118-31290 v43 a

The emerging metal-free carbon nitride (C3N4) offers prominent possibilities for realizing the highly effective hydrogen evolution reaction (HER). However, its poor surface conductivity and insufficient catalytic sites hinder the HER performance. Herein, a one-dimensional vermicular rope-like graphitic carbon nitride nanostructure is demonstrated that consists of multichannel tubular pores and high nitrogen content, which is fabricated through a cost-effective approach having the final stoichiometry g-C3N4.7 for HER application. The present g-C3N4.7 is unique owing to the presence of abundant channels for the diffusion process, modulated surface chemistry with rich- electroactive sites from N-electron lone pairs, greatly reduced recombination rate of photoexcited exciton pairs, and a high donor concentration (4.26 x 10(17) cm(3)). The catalyst offers a visible-light-driven photocatalytic H-2 evolution rate as high as 4910 mu mol h(-1)g(-1) with an apparent quantum yield of 14.07% at band gap absorption (2.59 eV, 479 nm) under 7.68 mW cm(-2) illumination. The number of hydrogen gas molecules produced is 1.307 x 10(15) s(-1) cm(-2), which remained constant for a minimum of 18 h of repeated cycling in the HER without any degradation of the catalyst. In density functional theory calculations, a significant change in the band offset is observed due to N doping into the system in favor of electron catalysis. The theoretical band gap of a monolayer of g-C3N4.7 was enormously reduced because of the presence of additional densities of states from the doped N atom inside the band gap. These impurity or donor bands are formed inside the band gap region, which ultimately enhance the hydrogen ion reduction reaction enormously.

10acarbon nitride10aDensity functional theory10ahydrogen evolution reaction10anitrogen-rich10aPhotocatalyst1 aAntil, Bindu1 aKumar, Lakshya1 aRanjan, Ravi1 aShenoy, Sulakshana1 aTarafder, Kartick1 aGopinath, Chinnakonda, S.1 aDeka, Sasanka uhttps://library.ncl.res.in/content/one-dimensional-multichannel-g-c3n47-nanostructure-realizing-efficient-photocatalytic02873nas a2200265 4500008004100000022001400041245015900055210006900214260000800283300001100291490000800302520192200310653002202232653003002254653002102284653002302305653001802328653002002346100002002366700002002386700003002406700002602436700002102462856012402483 2022 eng d a0925-838800aFacile fabrication of nano silver phosphate on B-doped g-C3N4: an excellent p-n heterojunction photocatalyst towards water oxidation and Cr (VI) reduction0 aFacile fabrication of nano silver phosphate on Bdoped gC3N4 an e cMAR a1628530 v8983 aA photostable Ag3PO4/BCN type-II p-n heterojunction has been demonstrated by loading nano Ag3PO4 on B-doped g-C3N4 nanosheet (BCN). The photocatalysts were successfully characterized by various physicochemical techniques and their photocatalytic activities were tested towards the water oxidation reaction to produce oxygen and Cr (VI) reduction under visible light. The HRTEM confirms Ag3PO4 with a particle size of 15 nm has been deposited on BCN to construct a p-n heterojunction. The BCNS-50 absorbs more visible light in the solar spectrum as compared to other catalyst, demonstrating the ability to generate 587 mu mol h(-1)g(-1) O-2 and reduces 98% of 20 ppm Cr (VI) solution in 1 h. The lower PL intensity as well as lower arc value in case of BCNS-50 suggests the maximum e-h separation and lower charge transfer resistance across the semiconductor/electrolyte interface. The BCN sheet provides a compact heterojunction where the oxidation peak of Ag3PO4 decreases gradually and disappear in case of BCNS-50 suggesting the enhance stability of Ag3PO4 in the heterojunction. BCNS-50 could able to produce -139 and 3087.5 mu A photocurrent both in cathodic and anodic direction which is approximately 7 and 2.4 folds higher as compared to nano Ag3PO4. The generation of photocurrent in both cathodic and anodic direction confirms the formation of p-n heterojunction which further supported by Mott-Schottky analysis. Furthermore the construction of the p-n heterojunction is verified via Mott-Schottky study. DFT calculation explains the contribution of various atomic orbital of Ag3PO4 and BCN towards the formation of hybrid orbital in the heterojunction and the path for charge delocalization between them. This work may provide a limelight and alternative pathway for enhanced photocatalytic performance on construction of the p-n heterojunction in a simple way. (C) 2021 Elsevier B.V. All rights reserved.10aCr (VI) reduction10aDensity functional theory10aInterfacial zone10ap-n heterojunction10aPhotocatalyst10aWater oxidation1 aSahoo, Mitarani1 aBabu, Pradeepta1 aSingh, Chandrodai, Pratap1 aKrishnamurty, Sailaja1 aParida, Kulamani uhttps://library.ncl.res.in/content/facile-fabrication-nano-silver-phosphate-b-doped-g-c3n4-excellent-p-n-heterojunction02219nas a2200229 4500008004100000022001400041245011500055210006900170260000800239300001100247490000800258520137100266653001501637653003101652653003001683653003001713653003101743100002701774700003001801700002601831856013201857 2023 eng d a0169-433200aChemically modified graphene sheets as potential sensors for organophosphate compounds(pesticide): A DFT study0 aChemically modified graphene sheets as potential sensors for org cMAY a1567450 v6193 a

Owing to the extensive use of pesticides in agriculture and the threat posed to the environment and humankind, attention is drawn toward the need for its remediation from various sources, in particular from water. The adsorption characteristics of hydrophobic graphene and its BN doped counterparts are evaluated using DFT methodology, to assess their sensing potential towards notable pesticide molecules (Organophosphate pesticides (OPs) such as chlorpyriphos, parathion, methyl-parathion, and fenitrothion). To accomplish this, various elec-tronic properties such as band structure, DOS, Bader charge analysis, and CDD have been calculated. Interest-ingly, exothermic interactions (-0.1 eV to-2 eV) have been noted for all the OPs with NB doped single vacancy defect induced graphene surfaces. With an exception of FTN, all the other OPs showed significant changes in the electronic properties of surfaces as apparent from the change in band gap and nature of the band from indirect to direct. The appreciable adsorption energy, higher charge transfer, and notable variation in the band gap are the decisive factors behind the strong interaction exhibited by NB doped surfaces especially dg-(NB-2)2 (except FTN). These findings demonstrate the suitability of NB doped single vacancy defect induced graphene sheets for the detection of the studied OPs.

10aAdsorption10aBN doped graphene surfaces10aCharge density difference10aDensity functional theory10aOrganophosphate pesticides1 aShivankar, Bhavana, R.1 aSingh, Chandrodai, Pratap1 aKrishnamurty, Sailaja uhttps://library.ncl.res.in/content/chemically-modified-graphene-sheets-potential-sensors-organophosphate-compoundspesticide-dft03170nas a2200301 4500008004100000022001400041245013900055210006900194260000800263300001600271490000700287520214300294653001302437653003002450653002902480653001402509653003002523653003302553100001902586700001802605700001802623700002502641700001702666700001602683700002502699700002002724856012402744 2023 eng d a1944-824400aMitigating dendrite formation on a Zn electrode in aqueous zinc chloride by the competitive surface chemistry of an imidazole additive0 aMitigating dendrite formation on a Zn electrode in aqueous zinc  cMAY a23093-231030 v153 a

Electrochemical energy storage systems are critical in several ways for a smooth transition from nonrenewable to renewable energy sources. Zn-based batteries are one of the promising alternatives to the existing state-of-the-art Li-ion battery technology, since Li-ion batteries pose significant drawbacks in terms of safety and cost-effectiveness. Zn (with a reduction potential of -0.76 V vs SHE) has a significantly higher theoretical volumetric capacity (5851 mAh/cm3) than Li (2061 mAh/cm3), and it is certainly far less expensive, safer, and more earth-abundant. The formation of dendrites, hydrogen evolution, and the formation of a ZnO passivation layer on the Zn anode are the primary challenges in the development and deployment of rechargeable zinc batteries. In this work, we examine the role of imidazole as an electrolyte additive in 2 M ZnCl2 to prevent dendrite formation during zinc electrodeposition via experimental (kinetics and imaging) and theoretical density functional theory (DFT) studies. To characterize the efficacy and to identify the appropriate concentration of imidazole, linear sweep voltammetry (LSV) and chronoamperometry (CA) are performed with in situ monitoring of the electrodeposited zinc. The addition of 0.025 wt % imidazole to 2 M ZnCl2 increases the cycle life of Zn-symmetric cells cycled at 1 mA/cm2 for 60 min of plating and stripping dramatically from 90 to 240 h. A higher value of the nucleation overpotential is noted in the presence of imidazole, which suggests that imidazole is adsorbed at a competitively faster rate on the surface of zinc, thereby suppressing the zinc electrodeposition kinetics and the formation. X-ray tomography reveals that a short circuit caused by dendrite formation is the main plausible failure mechanism of Zn symmetric cells. It is observed that the electrodeposition of zinc is more homogeneous in the presence of imidazole, and its presence in the electrolyte also inhibits the production of a passivating coating (ZnO) on the Zn surface, thereby preventing corrosion. DFT calculations conform well with the stated experimental observations.

10adendrite10aDensity functional theory10aexchange current density10aImidazole10aX-ray computed tomography10azinc metal electrodeposition1 aRana, Ashutosh1 aThakare, Anup1 aKumar, Nikhil1 aMukherjee, Buddhadev1 aTorris, Arun1 aDas, Bidisa1 aOgale, Satishchandra1 aBanerjee, Abhik uhttps://library.ncl.res.in/content/mitigating-dendrite-formation-zn-electrode-aqueous-zinc-chloride-competitive-surface02215nas a2200253 4500008004100000022001400041245013200055210006900187260000800256300001100264490000900275520129000284653001501574653004001589653002501629653003001654653002501684100002901709700003001738700002001768700001901788700002601807856012801833 2024 eng d a2210-271X00aIndazole-5-amine (AIA) as competing corrosion coating to Benzotriazole (BTAH) at the interface of Cu: A DFT and BOMD case study0 aIndazole5amine AIA as competing corrosion coating to Benzotriazo cSEP a1147620 v12393 a

This study compares three organic compounds-benzotriazole (BTAH), imidazole (IM), and indazole-5-amine (AIA)-as corrosion inhibitors for copper substrates. Using Density Functional Theory (DFT) and Born-Oppenheimer Molecular Dynamics (BOMD) calculations, it identifies AIA as a promising and cost-effective alternative to the toxic BTAH. The adsorption strength on Cu(1 0 0) surfaces is ranked AIA>BTAH>IM for both neutral and deprotonated forms. These findings are supported by electronic parameter studies, including Bader charge analysis, density of states (DOS), charge density differences (CDD), and frontier molecular orbital analysis. AIA shows the best adsorption in a parallel orientation at the top site. Packing studies reveal that hydrogen bonding stabilizes the interaction energies within self-assembled AIA aggregates. Organometallic complexation studies reveal that deprotonated BTAH exhibits higher interaction energy with a single Cu atom compared to AIA when bonded through the carbon end, consistent with the findings from BOMD studies. However, on periodic Cu surfaces, AIA outperforms BTAH molecules as seen from adsorption energies. This investigation highlights AIA's potential as a superior and more economical corrosion inhibitor for copper.

10aAdsorption10aBorn-Oppenheimer molecular dynamics10aCorrosion inhibition10aDensity functional theory10aIndazole derivatives1 aSamal, Pragnya, Paramita1 aSingh, Chandrodai, Pratap1 aTiwari, Shivani1 aShah, Vaishali1 aKrishnamurty, Sailaja uhttps://library.ncl.res.in/content/indazole-5-amine-aia-competing-corrosion-coating-benzotriazole-btah-interface-cu-dft-and02297nas a2200229 4500008004100000022001400041245010500055210006900160260000900229490000700238520147700245653003001722653002601752653002101778653002201799653003201821653001401853100002201867700002401889700002601913856012801939 2024 eng d a2352-152X00aQuasi-molecular hydrogen storage capacity of graphene quantum dots: A dispersion corrected DFT study0 aQuasimolecular hydrogen storage capacity of graphene quantum dot cAPR 0 v843 a

Efficient storage of hydrogen, green fuel with the highest energy density, remains a pressing challenge. Among the several materials investigated for their potential hydrogen storage, 2D materials, like graphene, have advantages such as mechanical strength and large surface area but fail to store hydrogen reversibly. In this context, the present computational experiment demonstrates the potential of Graphene Quantum Dots (GQDs) with 24, 40 and 42 carbon atoms for their hydrogen storage capacity in quasi-molecular mode. Factors such as edge terminations, heteroatom doping, and anchoring of metal atoms are evaluated as a function of their storage capacity. The study clearly demonstrates an enhanced storage capacity of quantum dots, particularly, when a single Ti adatom is anchored on a 24 carbon atom GQD with a storage weight % of 2.24 % w/w. The storage weight % is further noted to increase as a function of the number of Ti atoms anchored on the GQD with the highest hydrogen storage weight % of 6.1 % w/w. Importantly, the adsorption of hydrogen molecule on the Ti atom is through a quasi-molecular mode and is driven by Kubas interaction. This type of interactions makes GQDs as viable storage materials at room temperature. Secondly, the work demonstrates that GQDs offer higher storage capacities of hydrogen molecules as compared to their 2D counterparts viz., graphene sheets, making them attractive candidates to be explored experimentally.

10aDensity functional theory10agraphene quantum dots10aHydrogen storage10aKubas interaction10aQuasi -molecular adsorption10aTi adatom1 aKhadilkar, Pranav1 aSamudre, Nikhil, S.1 aKrishnamurty, Sailaja uhttps://library.ncl.res.in/content/quasi-molecular-hydrogen-storage-capacity-graphene-quantum-dots-dispersion-corrected-dft02385nas a2200205 4500008004100000022001400041245010100055210006900156260000900225490000700234520164100241653001301882653003101895653002201926653003001948653003501978100002502013700001702038856012402055 2024 eng d a1861-472800aRole of aromatic alcohol additives on asymmetric organocatalysis reactions: insights from theory0 aRole of aromatic alcohol additives on asymmetric organocatalysis cFEB 0 v193 a

The presence of an aromatic additive has been seen to enhance, often significantly, the enantioselectivity and yield in asymmetric organocatalysis. Considering their success across a dizzying range of organocatalysts and organic transformations, it would seem unlikely that a common principle exists for their functioning. However, the current investigations with DFT suggest a general principle: the phenolic additive sandwiches itself, through hydrogen bonding and pi & sdot;& sdot;& sdot;pi stacking, between the organocatalyst coordinated electrophile and nucleophile. This is seen for a wide range of experimentally reported systems. That such complex formation leads to enhanced stereoselectivity is then demonstrated for two cases: the cinchona alkaloid complex (BzCPD), catalysing thiocyanation (2-naphthol additive employed), as well as for L-pipecolicacid catalysing the asymmetric nitroaldol reaction with a range of nitro-substituted phenol additives. These findings, indicating that dual catalysis takes place when phenolic additives are employed, are likely to have a significant impact on the field of asymmetric organocatalysis. The current DFT based study, on a wide range of organocatalysis systems, reveals a general principle by which phenolic additives influence asymmetric organocatalysis reactions. It is shown that the phenolic additive forms a sandwich complex, through hydrogen bonding and pi & sdot;& sdot;& sdot;pi stacking interactions, with the organocatalyst coordinated electrophile and nucleophile, and enhances the enantioselectivity of the system as a result. image

10aAdditive10aAsymmetric Organocatalysis10aCinchona Alkaloid10aDensity functional theory10aEnantioselective Thiocyanation1 aBanerjee, Subhrashis1 aVanka, Kumar uhttps://library.ncl.res.in/content/role-aromatic-alcohol-additives-asymmetric-organocatalysis-reactions-insights-theory02578nas a2200217 4500008004100000022001400041245015200055210006900207260000800276490000700284520173800291653003002029653003702059653003002096653001702126100002502143700002202168700002602190700001802216856012602234 2024 eng d a0934-086600aUltra-small Au nanoclusters with tailored photoluminescence properties using modified thiol ligands: a computational and experimental demonstration0 aUltrasmall Au nanoclusters with tailored photoluminescence prope cOCT0 v413 a

Au nanoclusters with tailored photoluminescence can be obtained through controlled nanoparticle ligand interface chemistry. The present work reports molecular gold nanoclusters with tuneable photoluminescence emission from 600 to 700 nm using N,N `,N `'-trialkyl (11-mercaptoundecyl)ammonium chloride ligands as capping-agents. The tunability within red spectral region is regulated through specific interface chemistry between gold nanoclusters of molecular range and functional groups of the quaternary ammonium head over N,N `,N `'-trialkyl(11-mercaptoundecyl)ammonium chloride. Combined understanding obtained from the spectroscopy, microscopy, and density functional theory studies demonstrate that the functional group specific electronic interactions at the interfaces steer the emission characteristics of ``molecular'' Au nanoparticles. The study clearly identifies that bulkier functional groups, i.e., triethyl, tripropyl, tributyl, and dimethyl benzene over N+ (of thiol ligand) through their steric effects minimize the particle size giving rise to tunable photoluminescence emission in red spectral region. However, the red shift seen in the emission Au nanoclusters with N-(11-mercaptoundecyl)-N,N `-dimethylbenzenammonium chloride ligand in contradiction to particle size effect is computationally proved to be due to the delocalization of electron density from benzene aromatic ring to N+ of ammonium head leading to a reduction in the HOMO-LUMO energy gap. Fluorescence properties of water dispersible Au nanoclusters are tuned by varying the ammonium head group. Density Functional Theory studies correlate the distinction in emission when head group is phenyl to charge transfer characteristics. image

10aDensity functional theory10aphotoluminescent Au nanoclusters10asurface plasmon resonance10athiol ligand1 aChahande, Anurag, M.1 aMaibam, Ashakiran1 aKrishnamurty, Sailaja1 aDevi, Nandini uhttps://library.ncl.res.in/content/ultra-small-au-nanoclusters-tailored-photoluminescence-properties-using-modified-thiol01738nas a2200241 4500008004100000022001400041245014600055210006900201260000900270300001100279490000800290520089800298653003001196653001301226653002301239653002201262100001701284700001801301700001101319700001901330700001801349856012901367 2024 eng d a0038-109800aUnveiling electronic structure and magnetic properties of AFe2O4 (A = Co, Ni, Zn, and Mg): Synergizing experimentation with DFT investigation0 aUnveiling electronic structure and magnetic properties of AFe2O4 cAPR  a1154590 v3823 a

This study presents the synthesis of nano-crystalline spinel ferrites AFe2O4 (A = Co2+, Ni+2, Zn+2, and Mg+2), through the sol-gel method, yielding crystallite sizes ranging from 12 to 28 nm. The variation in IR and Raman spectra due to M-O-M bonding supports the variation in lattice parameters. The magnetization measurements revealed that CoFe2O4 has a high saturation magnetization of -55 emu/g and coercivity of -1350 Oe, while ZnFe2O4 exhibited saturation magnetization value of -8 emu/g and coercivity of -16 Oe. In addition, the electronic structure calculated using DFT, which corroborated the antiparallel alignment of Fe ions in the tetrahedral and octahedral sites, validating the measured magnetic moments. Notably, the CoFe2O4 ferrite exhibited a higher squareness ratio than other ferrites, signifying its suitability as a magnetic material for audiovideo recording.

10aDensity functional theory10aFerrites10aMagnetic materials10aX-ray diffraction1 aDhaka, Saroj1 aShukla, Aarti1 aGarima1 aPoonia, Kavita1 aKumar, Sudesh uhttps://library.ncl.res.in/content/unveiling-electronic-structure-and-magnetic-properties-afe2o4-co-ni-zn-and-mg-synergizing01252nas a2200241 4500008004100000022001400041245008400055210006900139260000800208490000700216520048300223653002300706653003000729653001400759653001400773653001600787100002300803700002000826700002700846700001900873700001900892856009900911 2025 eng d a1434-194800aC=C insertion over N=C=O of allyl isocyanate into the Ge-Si bond of a germylene0 aCC insertion over NCO of allyl isocyanate into the GeSi bond of  cSEP0 v283 a

Two isocyanates are reacted with the germylene, PhC(NtBu)(2)Ge-Si(SiMe3)(3) (1). Phenyl isocyanate undergoes catalytic cyclotrimerization with 1 leading to 1,3,5-triphenyl isocyanurate (2), while allyl isocyanate undergoes both cyclotrimerization and the C=C bond insertion between the Ge-Si bond. The constitution of 3 is determined by single-crystal X-ray studies. The contrasting reactivity pattern is explained by comprehensive density functional theory studies.

10aCyclotrimerization10aDensity functional theory10aGermylene10aInsertion10aisocyanates1 aAjithkumar, V., S.1 aKhilari, Nripen1 aGhanwat, Pratiksha, B.1 aKoley, Debasis1 aSen, Sakya, S. uhttps://library.ncl.res.in/content/cc-insertion-over-nco-allyl-isocyanate-ge-si-bond-germylene01403nas a2200325 4500008004100000022001400041245011300055210006900168260000900237300001100246490000800257520032000265653003000585653003500615653002600650653000900676653002600685653002500711100002000736700002100756700002700777700001900804700002000823700002000843700002000863700002600883700002000909700002200929856012600951 2025 eng d a0304-885300aElectronic, magnetic, and mechanical properties of co-doped GaSb: A promising diluted magnetic semiconductor0 aElectronic magnetic and mechanical properties of codoped GaSb A  cNOV  a1734990 v6323 a

{Understanding the interplay between magnetism and the electronic structure is crucial for the development of novel spintronic materials. This study employs density functional theory (DFT) calculations to investigate these properties in cubic Gallium Antimonide (GaSb) doped with Cobalt (Co) (Ga1-xCoxSb

10aDensity functional theory10aDilute magnetic semiconductors10aElectronic properties10aGaSb10amechanical properties10aSpintronic materials1 aSamant, Ramnath1 aSaraf, Deepashri1 aAdhikari, Rajendra, P.1 aShilkar, Omkar1 aRaikar, Sakshit1 aSilveira, Allan1 aSawant, Manthan1 aSappati, Subrahmanyam1 aJoshi, Niharika1 aDesai, Ashish, M. uhttps://library.ncl.res.in/content/electronic-magnetic-and-mechanical-properties-co-doped-gasb-promising-diluted-magnetic01811nas a2200217 4500008004100000022001400041245011200055210006900167260000800236300001100244490000800255520103100263653002301294653003001317653002601347653001901373653003001392100002401422700002201446856012501468 2025 eng d a0301-010400aEvaluating the catalytic potential of Lithium-decorated graphene quantum dots for small molecule activation0 aEvaluating the catalytic potential of Lithiumdecorated graphene  cJUL a1126820 v5953 a

The search for effective catalysts in small molecule activation has intensified as industries seek efficient and costeffective solutions. Lithium (Li), known for its unique electronic properties, is of significant interest as a catalyst. However, its specific catalytic potential when anchored on graphene quantum dots (GQDs) has not been fully explored. This study investigates the catalytic potential of lithium (Li) adatoms on GQDs with various edge conformations (zigzag and armchair) and sizes (24 and 42 atoms). Using density functional theory (DFT), we examine the interactions of Li-decorated GQDs with small molecules such as H2, N2, CO, O2, and CO2. Our findings reveal that Li-GQD complexes exhibit optimal catalytic activity for all these molecules, based on binding energy, charge distribution, and bond length changes. The smallest GQD, coronene (24 carbon atoms), shows the most promising catalytic activity, providing experimental leads for synthesizing and testing efficient Li-anchored catalysts.

10aCatalytic activity10aDensity functional theory10agraphene quantum dots10aLithium adatom10asmall molecule activation1 aSamudre, Nikhil, S.1 aTiwari, Rukminesh uhttps://library.ncl.res.in/content/evaluating-catalytic-potential-lithium-decorated-graphene-quantum-dots-small-molecule02579nas a2200289 4500008004100000022001400041245013400055210006900189260000900258300001000267490000700277520160400284653002201888653003001910653001601940653001401956653001301970100002501983700002202008700002302030700002002053700002802073700002502101700001502126700002202141856012602163 2025 eng d a2045-232200aSynthesis, characterization, computational and biological evaluation of pyrazole hydrazones as promising anti-inflammatory agents0 aSynthesis characterization computational and biological evaluati cNOV  a422060 v153 a

In this study, two pyrazole-based hydrazone derivatives, 5-methyl-1-phenyl-4-(1-(2-phenylhydrazineylidene)ethyl)-1H-pyrazole (PMPH) and 1-(4-fluorophenyl)-5-methyl-4-(1-(2-phenylhydrazineylidene)ethyl)-1H-pyr azole (4F-PMPH), were synthesized and the structures of the compounds were elucidated through FT-IR, 1H and 13C NMR, and mass spectral methods. The anti-inflammatory potential was evaluated using the bovine serum albumin denaturation assay, with PMPH and 4F-PMPH showing maximum inhibition at 0.5 mg/mL, respectively, suggesting that fluorine substitution enhances bioactivity. Molecular docking studies against COX-II (PDB: 3LN1) revealed favorable binding energies of - 7.21 kcal/mol (PMPH) and - 8.03 kcal/mol (4F-PMPH). Molecular dynamics simulation of the best docked compound 4F-PMPH with COX-II (PDB: 3LN1) revealed a stable complex over a 100 ns simulation, supporting its potential as a promising inhibitor. In silico ADME analyses revealed pharmacokinetic behavior and drug-likeness. A comparative Density functional theory-based spectroscopic and electronic investigation was conducted using the B3LYP/6-31G(d,p) level of theory. Vibrational frequency analysis showed strong correlation between theoretical and experimental IR spectra. Frontier molecular orbital analysis, molecular electrostatic surface potential maps, Mulliken charges, electronic and global reactivity parameters were also studied. Besides, reduced density gradient, non-covalent interaction, electron localization function, and localized orbital locator maps were analyzed for both the compounds.

10aAnti-inflammatory10aDensity functional theory10aDrug design10aHydrazone10aPyrazole1 aDeshmukh, Hemant, S.1 aAdole, Vishnu, A.1 aFrit, Alfind, Paul1 aMali, Suraj, N.1 aYasin, Haya, Khader Ahm1 aPatil, Bhausaheb, N.1 aJanani, S.1 aJagdale, Bapu, S. uhttps://library.ncl.res.in/content/synthesis-characterization-computational-and-biological-evaluation-pyrazole-hydrazones02711nas a2200301 4500008004100000022001400041245013500055210006900190260000900259300001100268490000800279520168000287653001801967653003001985653002802015653002402043653001602067653002002083100002802103700001902131700001902150700002102169700002302190700002602213700001602239700002502255856012902280 2026 eng d a2468-823100aEffect of sulfonation density on acid strength in ion exchange resins: Insights from solid-state NMR and density functional theory0 aEffect of sulfonation density on acid strength in ion exchange r cMAR  a1157940 v5933 a

Ion-exchange (IE) resins are widely used as solid acid catalysts; however, their surface acidity remains poorly characterized because their limited thermal stability precludes conventional NH3-based acidity measurements. Moreover, acid-site accessibility in IE resins is strongly governed by solvent- or reactant-induced swelling. Here, we investigate the surface acidity of commercial Amberlyst and Indion IE resins using & sup3;& sup1;P MAS NMR (Magic Angle Spinning Nuclear Magnetic Resonance), employing TMPO as a molecular probe dispersed on the resin with moderately swelling dichloromethane, thereby capturing the swollen-state acidity relevant for predicting catalytic activity. The deconvolution of the P-31 MAS NMR spectra reveals three distinct acid-strength zones arising from inhomogeneous sulfonation of the polymer matrix. The overall acidity, quantified by the area-weighted average P-31 chemical shift (delta), increases monotonically with sulfonation density. Notably, only resins containing acid sites stronger than similar to 80 ppm exhibited measurable catalytic activity in alpha-pinene isomerization, establishing a direct correlation between acidity and activity. Density functional theory (DFT) calculations on representative resin models, supported by electron-density analyses, attribute the enhancement of acid strength at higher sulfonation densities to cooperative hydrogen-bonding networks among neighboring sulfonic acid groups. Together, these findings establish P-31 MAS NMR-derived surface acidity as a catalytically relevant descriptor for the rational selection of IE resins in liquid phase acid-catalyzed chemistries.

10aAcid strength10aDensity functional theory10aheterogeneous catalysis10aIon-exchange resins10aSolid acids10aSolid-state NMR1 aTumulu, Goutam, Narayan1 aDatar, Sarvesh1 aShelke, Ankita1 aSwain, Gitanjali1 aAjithkumar, T., G.1 aThirumalaiswamy, Raja1 aMohan, Ojus1 aMahajani, Sanjay, M. uhttps://library.ncl.res.in/content/effect-sulfonation-density-acid-strength-ion-exchange-resins-insights-solid-state-nmr-and02379nas a2200349 4500008004100000022001400041245013700055210006900192260000900261300001100270490000900281520118000290653000601470653002701476653003701503653003301540653003001573653002801603653003701631100002601668700001801694700001701712700002401729700001801753700002201771700002401793700002101817700002001838700002101858700002101879856012901900 2026 eng d a0022-286000aStructural characterisation, anticancer properties, and BSA binding of 2,6-dipyrazinylpyridines: Insights from experiment and theory0 aStructural characterisation anticancer properties and BSA bindin cFEB  a1442250 v13513 a

The phenyl-(2,6-di-2-pyrazinyl)pyridine derivatives (L1, L2) were synthesized using a one-pot Krohnke-type method, starting from 2-acetylpyrazine and substituted benzaldehydes. Their structures were characterized using a combination of spectroscopic (NMR, HRMS) and single-crystal X-ray diffraction techniques, complemented by density functional theory (DFT). Single-crystal X-ray diffraction reveals that L1 crystallizes in the C2/c space group (T = 296 K) with its supramolecular assembly being stabilized by C-H & ctdot;N and pi-pi stacking interactions, whereas L2 facilitates C-H & ctdot;N, N-H & ctdot;pi bifurcated, and pi-pi* interactions. The bio-interaction properties of L1 were studied using fluorescence spectroscopy with bovine serum albumin (BSA) as a model protein. Fluorescence studies demonstrated L1 induces static quenching of BSA, with a binding constant of 5.15 x 104 mol & sdot;dm-3. Synchronous and three-dimensional fluorescence spectra further demonstrated that L1 brings forth significant conformational changes in BSA. The compounds were evaluated for cytotoxicity against the HCT-116 human colorectal cancer cell line.

10a210a6-dipyrazinylpyridines10aBovine serum albumin interaction10aCytotoxicity (HCT-116 cells)10aDensity functional theory10aHalogenated derivatives10aSingle-crystal X-ray diffraction1 aEnumula, Sreenivasulu1 aShaikh, Javed1 aShaikh, Amin1 aSheikh, Kounsar, N.1 aTambe, Pranav1 aLande, Dipali, N.1 aGejji, Shridhar, P.1 aShaligram, Parth1 aGonnade, Rajesh1 aBhadbhade, Mohan1 aAhmed, Khursheed uhttps://library.ncl.res.in/content/structural-characterisation-anticancer-properties-and-bsa-binding-26-dipyrazinylpyridines