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Obtaining Molecular Thermochemistry From Calculations

Published

Author(s)

Karl K. Irikura

Abstract

There are several computational approaches for predicting gas-phase, molecular thermochemistry. For common organic compounds, empirical methods are quick to compute and have been effectively parameterized. For uncommon compounds, the relative robustness of ab initio methods compensates their moderate or high computational costs. Intermediate situations may be addressed using semiempirical molecular orbital theory. When using ab initio methods for predicting thermochemistry, a good choice of working reaction provides dramatically improved reliability. At the opposite extreme, atomization reactions are only compatible with high-level, composite, parameterized methods. Some simple guidelines are helpful for designing good working reactions and for identifying molecules for which ab initio methods may perform poorly.
Citation
Obtaining Molecular Thermochemistry From Calculations
Volume
42
Publisher Info
Book Chapter Comprehensive Kinetics series (Elsevier), Volume Editors: R.W. Carr and M.R. Zachariah,

Keywords

Ab initio, computational chemistry, density functional theory, kinetics, quantum chemistry, semiempirical, thermochemistry

Citation

Irikura, K. (2007), Obtaining Molecular Thermochemistry From Calculations, Book Chapter Comprehensive Kinetics series (Elsevier), Volume Editors: R.W. Carr and M.R. Zachariah, (Accessed December 4, 2023)
Created September 30, 2007, Updated February 17, 2017