@article {48762,
	title = {Effect of charge and solvation shell on non-radiative decay processes in s-block cationic metal ion water clusters},
	journal = {Journal of Chemical Physics},
	volume = {159},
	year = {2023},
	month = {AUG },
	pages = {054304},
	type = {Article},
	abstract = {<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{\textquoteright}s ionization potential (IP) exceeds the system{\textquoteright}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{\textquoteright}s decay is possible for n \&gt;= 2 in Na+-(H2O)(n) clusters. Our findings highlight the influence of metal ions{\textquoteright} 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>
},
	issn = {0021-9606},
	doi = {10.1063/5.0153598},
	author = {Kumar, Ravi and Ghosh, Aryya and Vaval, Nayana}
}
@article {48755,
	title = {Enhancing diradical character of chichibabin{\textquoteright}s hydrocarbon through fluoride substitution},
	journal = {ChemPlusChem},
	volume = {88},
	year = {2023},
	month = {AUG},
	pages = {e202300273},
	type = {Article},
	abstract = {<p>
	In this work, 5-SIDipp [SIDipp=1,3-bis(2,6-diisopropylphenyl)-imidazolin-2-ylidene] (1) derived Chichibabin{\textquoteright}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{\textquoteright}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{\textquoteright}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>
},
	keywords = {C-F Bond Activation, Chichibabin \& PRIME, DFT, N-Heterocyclic carbene, s Hydrocarbon},
	issn = {2192-6506},
	doi = {10.1002/cplu.202300273},
	author = {Kundu, Gargi and Dash, Soumya Ranjan and Kumar, Ravi and Vanka, Kumar and Ghosh, Aryya and Sen, Sakya S.}
}
