01926nas a2200169   4500008004100000022001400041245011900055210006900174260000900243300001100252490000800263520130400271100001601575700001701591700001801608856013001626       2023                        eng d  a0021-960600aEffect of charge and solvation shell on non-radiative decay processes in s-block cationic metal ion water clusters0 aEffect of charge and solvation shell on nonradiative decay proce  cAUG   a0543040 v1593 a<p>
	Intermolecular Coulombic decay or electron transfer-mediated decay are the autoionization processes through which a molecule can relax. This relaxation is only possible if the inner valence's ionization potential (IP) exceeds the system's double ionization potential (DIP). To study the effects of charge and solvation shell, we have calculated the IP, DIP values, and lifetime of Na-2s and Mg-2s temporary bound states in various optimized structures of Na+-(H2O)(n) and Mg2+-(H2O)(n) (n = 1-5) micro-solvated clusters, where n water molecules are distributed in a way that some are directly bound to the metal ion and the rest to the water molecules. The first and second solvation shells are the names for the former and the latter water-binding positions, respectively. For a given n, the lifetime of decaying states is longer when water molecules are in the second solvation shell. We found that the Mg-2p state can decay for all n values in Mg2+-(H2O)(n) clusters, whereas the Na-2p state's decay is possible for n &gt;= 2 in Na+-(H2O)(n) clusters. Our findings highlight the influence of metal ions' charge, different solvation shell structures, and the number of water molecules on the decay rate. These systems are relevant to the human body, which makes this study significant.</p>
1 aKumar, Ravi1 aGhosh, Aryya1 aVaval, Nayana  uhttps://library.ncl.res.in/content/effect-charge-and-solvation-shell-non-radiative-decay-processes-s-block-cationic-metal-ion01858nas a2200265   4500008004100000022001400041245009300055210006900148260000800217300001500225490000700240520100900247653002401256653002401280653000801304653002701312653001801339100001701357700002501374700001601399700001701415700001701432700001901449856012401468       2023                        eng d  a2192-650600aEnhancing diradical character of chichibabin's hydrocarbon through fluoride substitution0 aEnhancing diradical character of chichibabins hydrocarbon throug  cAUG  ae2023002730 v883 a<p>
	In this work, 5-SIDipp [SIDipp=1,3-bis(2,6-diisopropylphenyl)-imidazolin-2-ylidene] (1) derived Chichibabin's hydrocarbon with an octafluorobiphenylene spacer (3) has been reported. The addition of two equivalents of 5-SIDipp with decafluorobiphenyl in presence of BF3 gives the double C-F bond activated imidazolium salt with two tetrafluoroborate anions, 2. Further reduction of 2 gives the fluorine substituted 5-SIDipp based Chichibabin's hydrocarbon, 3. Quantum chemical calculations suggested a singlet state of 3 with a singlet-triplet energy gap (?ES-T) of 3.7 kcal mol(-1), which is substantially lower with respect to the hydrogen substituted NHC-based Chichibabin's hydrocarbons (10.7 kcal mol(-1), B3LYP). As a result, the diradical character (y) of 3 (y=0.62) is also noticeably higher than the hydrogen substituted CHs (y=0.41-0.43). The ?ES-T was found to be higher in CASSCF (22.24 kcal mol(-1)) and CASPT2 (11.17 kcal mol(-1)) for 3 and the diradical character (d) is 44.6 %.</p>
10aC-F Bond Activation10aChichibabin & PRIME10aDFT10aN-Heterocyclic carbene10as Hydrocarbon1 aKundu, Gargi1 aDash, Soumya, Ranjan1 aKumar, Ravi1 aVanka, Kumar1 aGhosh, Aryya1 aSen, Sakya, S.  uhttps://library.ncl.res.in/content/enhancing-diradical-character-chichibabins-hydrocarbon-through-fluoride-substitution