Hydrogen bonding in substituted formic acid dimers

Senthilkumar, L. ; Ghanty, Tapan K. ; Ghosh, Swapan K. ; Kolandaivel, P. (2006) Hydrogen bonding in substituted formic acid dimers Journal of Physical Chemistry A, 110 (46). pp. 12623-12628. ISSN 1089-5639

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Official URL: http://pubs.acs.org/doi/abs/10.1021/jp061285q

Related URL: http://dx.doi.org/10.1021/jp061285q


The hydrogen-bonded dimers of formic acid derivatives XCOOH (X = H, F, Cl, and CH3) have been investigated using density functional theory (B3LYP) and second-order Moller-Plesset perturbation (MP2) methods, with the geometry optimization carried out using 6-311++G(2d,2p) basis set. The dimerization energies calculated using aug-cc-pVXZ (with X = D and T) basis have been extrapolated to infinite basis set limit using the standard methodology. The results indicate that the fluorine-substituted formic acid dimer is the most stable one in comparison to the others. Topological analysis carried out using Bader's atoms in molecules (AIM) theory shows good correlation of the values of electron density and its Laplacian at the bond critical points (BCP) with the hydrogen bond length in the dimers. Natural bond orbital (NBO) analysis carried out to study the charge transfer from the proton acceptor to the antibonding orbital of the X-H bond in the complexes reveals that most of the dimers are associated with conventional H-bonding except a few, where improper blue-shifting hydrogen bonds are found to be present.

Item Type:Article
Source:Copyright of this article belongs to American Chemical Society.
ID Code:11209
Deposited On:09 Nov 2010 03:49
Last Modified:02 Jun 2011 09:46

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