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Wiley, Journal of Computational Chemistry, 3(24), p. 298-309, 2003

DOI: 10.1002/jcc.10145

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Ground and excited state CASPT2 geometry optimizations of small organic molecules

Journal article published in 2003 by Christopher S. Page, Massimo Olivucci ORCID
This paper was not found in any repository, but could be made available legally by the author.
This paper was not found in any repository, but could be made available legally by the author.

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Abstract

A method for computing second-order multiconfigurational perturbation theory (CASPT2) energy gradients numerically has been implemented and applied to a range of elementary organic chromophores, including 1,3 butadiene, acrolein, and two protonated Schiff bases. Geometries of ground and excited states-as well as conical intersections-are compared with the corresponding CASSCF structures, illustrating the effect of including the correction for dynamical electron correlation. It is shown that the differences between the two methods are not readily categorized, but that, while individual changes in bond lengths can be quite large ( approximately 0.01-0.02 A), the natures and CASPT2 energetics of the structures remain similar. Exceptions to this tend to be systems that have a strong ionic character and that are not well described at the CASSCF level. Basis set effects (double- vs. triple-zeta) were examined for a limited number of examples, and found to be quite dramatic at both levels of theory.