Ab initio calculations on halogen-bonded complexes and comparison with density functional methods

A systematic theoretical investigation on a series of dimeric complexes formed between some halocarbon molecules and electron donors has been carried out by employing both ab initio and density functional methods. Full geometry optimizations are performed at the Moller-Plesset second-order perturbat...

Full description

Saved in:
Bibliographic Details
Published in:Journal of computational chemistry 2009-04, Vol.30 (5), p.725-732
Main Authors: Lu, Yun-Xiang, Zou, Jian-Wei, Fan, Ji-Cai, Zhao, Wen-Na, Jiang, Yong-Jun, Yu, Qing-Sen
Format: Article
Language:English
Subjects:
ab initio
Ammonia - chemistry
Binding sites
Chemistry
Comparative analysis
density functional methods
Electrons
Formaldehyde - chemistry
halogen bonding
Hydrocarbons, Halogenated - chemistry
Models, Chemical
Models, Molecular
Molecules
Quantum Theory
Thermodynamics
Water - chemistry
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary:A systematic theoretical investigation on a series of dimeric complexes formed between some halocarbon molecules and electron donors has been carried out by employing both ab initio and density functional methods. Full geometry optimizations are performed at the Moller-Plesset second-order perturbation (MP2) level of theory with the Dunning's correlation-consistent basis set, aug-cc-pVDZ. Binding energies are extrapolated to the complete basis set (CBS) limit by means of two most commonly used extrapolation methods and the aug-cc-pVXZ (X = D, T, Q) basis sets series. The coupled cluster with single, double, and noniterative triple excitations [CCSD(T)] correction term, determined as a difference between CCSD(T) and MP2 binding energies, is estimated with the aug-cc-pVDZ basis set. In general, the inclusion of higher-order electron correlation effects leads to a repulsive correction with respect to those predicted at the MP2 level. The calculations described herein have shown that the CCSD(T) CBS limits yield binding energies with a range of -0.89 to -4.38 kcal/mol for the halogen-bonded complexes under study. The performance of several density functional theory (DFT) methods has been evaluated comparing the results with those obtained from MP2 and CCSD(T). It is shown that PBEKCIS, B97-1, and MPWLYP functionals provide accuracies close to the computationally very expensive ab initio methods.
ISSN:0192-8651
1096-987X
DOI:10.1002/jcc.21094