Keyword search (4,164 papers available)

"Varadwaj A" Authored Publications:

Title Authors PubMed ID
1 DFT-B3LYP, NPA-, and QTAIM-based study of the physical properties of [M(II)(H2O)2(15-crown-5)] (M = Mn, Fe, Co, Ni, Cu, Zn) complexes Varadwaj PR; Varadwaj A; Marques HM; 21568260
CHEMBIOCHEM
2 Conformational analysis of 18-azacrown-6 and its bonding with late first transition series divalent metals: insight from DFT combined with NPA and QTAIM analyses Varadwaj PR; Varadwaj A; Peslherbe GH; Marques HM; 21961695
CERMM
3 An electronic structure theory investigation of the physical chemistry of the intermolecular complexes of cyclopropenylidene with hydrogen halides Varadwaj PR; Varadwaj A; Peslherbe GH; 22696309
CERMM
4 Can a single molecule of water be completely isolated within the subnano-space inside the fullerene C60 cage? A quantum chemical prospective Varadwaj A; Varadwaj PR; 23090782
CERMM

 

Title:An electronic structure theory investigation of the physical chemistry of the intermolecular complexes of cyclopropenylidene with hydrogen halides
Authors:Varadwaj PRVaradwaj APeslherbe GH
Link:https://pubmed.ncbi.nlm.nih.gov/22696309/
DOI:10.1002/jcc.23043
Publication:Journal of computational chemistry
Keywords:
PMID:22696309 Category: Date Added:2012-06-15
Dept Affiliation: CERMM
1 Centre for Research in Molecular Modeling, Department of Chemistry & Biochemistry, Concordia University, 7141 Sherbrooke Street West, Montréal, Québec H4B 1R6, Canada. pradeep@cermm.concordia.ca

Description:

The proton accepting and donating abilities of cyclopropenylidene (c-C(3)H(2)) on its complexation with hydrogen halides H-X (X = F, Cl, Br) are analyzed using density-functional theory with three functionals (PBE0, B3LYP, and B3LYP-D) and benchmarked against second-order Møller-Plesset (MP2) theory. Standard signatures including, inter alia, dipole moment enhancement, charge transfer from the carbenic lone pair to the antibonding s*(H-X) orbital, and H-X bond elongation are examined to ascertain the presence of hydrogen bonding in these complexes. The latter property is found to be accompanied with a pronounced red shift in the bond stretching frequency and with a substantial increase in the infrared intensity of the band on complex formation. The MP2/aug-cc-pVTZ c-C(3)H(2)···H-F complex potential energy surface turns out to be an asymmetric deep single well, while asymmetric double wells are found for the c-C(3)H(2)···H-Cl and c-C(3)H(2)···H-Br complexes, with an energy barrier of 4.1 kcal mol(-1) for proton transfer along the hydrogen bond in the latter complex. Hydrogen-bond energy decomposition, with the reduced variational space self-consistent field approach, indicates that there are large polarization and charge-transfer interactions between the interacting partners in c-C(3)H(2)···H-Br compared to the other two complexes. The C···H bonds are found to be predominantly ionic with partial covalent character, unveiled by the quantum theory of atoms in molecules. The present results reveal that the c-C(3)H(2) carbene divalent carbon can act as a proton acceptor and is responsible for the formation of hydrogen bonds in the complexes investigated.





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