01858nas a2200229 4500008004100000022001400041245010400055210006900159260007300228300001200301490000800313520098400321653001801305653004001323653003001363653002201393653002501415100002401440700002601464700001601490856012201506 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 uhttp://library.ncl.res.in/content/first-principle-investigation-thermal-stability-golden-fullerene-case-study-au-32-003074nas a2200265 4500008004100000022001400041245008500055210006900140260009200209300001200301490000700313520211500320653001902435653002602454653003002480653002202510653002802532653003002560653001602590100001702606700002602623700001702649700002702666856011502693 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 uhttp://library.ncl.res.in/content/dft-based-assay-tailor-made-terpyridine-ligand-metal-complexation-properties02700nas a2200265 4500008004100000022001400041245016000055210006900215260000800284300001100292490000800303520172400311653003002035653003202065653001702097653001902114653003702133100002202170700001902192700001702211700002502228700002602253700002702279856012802306 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 uhttp://library.ncl.res.in/content/unravelling-distinct-surface-interactions-modified-graphene-nanostructures-methylene-blue02872nas a2200265 4500008004100000022001400041245015900055210006900214260000800283300001100291490000800302520192200310653002202232653003002254653002102284653002302305653001802328653002002346100002002366700002002386700003002406700002602436700002102462856012302483 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 uhttp://library.ncl.res.in/content/facile-fabrication-nano-silver-phosphate-b-doped-g-c3n4-excellent-p-n-heterojunction02218nas a2200229 4500008004100000022001400041245011500055210006900170260000800239300001100247490000800258520137100266653001501637653003101652653003001683653003001713653003101743100002701774700003001801700002601831856013101857 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 uhttp://library.ncl.res.in/content/chemically-modified-graphene-sheets-potential-sensors-organophosphate-compoundspesticide-dft02296nas a2200229 4500008004100000022001400041245010500055210006900160260000900229490000700238520147700245653003001722653002601752653002101778653002201799653003201821653001401853100002201867700002401889700002601913856012701939 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 uhttp://library.ncl.res.in/content/quasi-molecular-hydrogen-storage-capacity-graphene-quantum-dots-dispersion-corrected-dft