Indian Journal of Advances in Chemical Science Volume: 5, Issue: 3, July 2017


ISSN No.: 2320-0898 (Print); 2320-0928 (Electronic)

DOI:  10.22607/IJACS.2017.503012



Research Article


      Ground State Sodium Cation Affinities and Associate Parameter of a Series of α,β-unsaturated Carbonyl Compounds of Type-2-Alkene Chemical Class (ACL, HNE, MVK, ACR, MA, and EMA): A Comparative DFT-Based Computational Study in Both Gas and Solvent Phase    
Biswarup Mandal, Bhudeb Ranjan De, Umasankar Senapati*
A detailed quantum mechanical study of ground state sodium cation (Na+) affinities (SCA) and some associated parameters of conjugated α,β-unsaturated carbonyl compounds (acrolein [ACL], 4-hydroxy-2-nonenal [HNE], methyl vinyl ketone [MVK], acrylamide [ACR], methyl acrylate [MA], and ethyl methacrylate [EMA]) has been computed in gas phase and in different solvents (water, dimethyl sulfoxide, CCl4) phase using DFT [B3LYP] method employing 6-311G (d,p) basis set. Sodium complexes are stabilized by solvation in all cases. ACR exhibits the highest SCA in all medium. In gas phase, computed Na+ affinity of the compounds are in following order ACR > MA > HNE > MVK ≥ EMA > ACL whereas upon solvation it shows different trend, follow ACR ≥ MA > EMA ≥ MVK> ACL ≥ HNE order. Sodium cation basicity (SCB) has been calculated from Gibbs free energies obtained in frequency calculation at the same level of theory. Calculated SCA and SCB values in gas phase are higher in comparison to the solvent phases. Entropy of the complex formation reactions has been estimated. Atomic charges of the complexes have been calculated in two schemes Mulliken population analysis and natural population analysis. The interactions sodium cation (Na+) with ligand is electrostatic ion-dipole interaction in all case. The local stereochemical disposition of the Na+ is found to be almost same in each case.

Key words: Unsaturated, Sodium cation affinities, Sodium cation basicity, Aqueous, B3LYP, DFT.



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