Potential Energy Surface of the Chromium Dimer Re-re-revisited with Multiconfigurational Perturbation Theory

Summary, in English

The chromium dimer has long been a benchmark molecule to evaluate the performance of different computational methods ranging from density functional theory to wave function methods. Among the latter, multiconfigurational perturbation theory was shown to be able to reproduce the potential energy surface of the chromium dimer accurately. However, for modest active space sizes, it was later shown that different definitions of the zeroth-order Hamiltonian have a large impact on the results. In this work, we revisit the system for the third time with multiconfigurational perturbation theory, now in order to increase the active space of the reference wave function. This reduces the impact of the choice of zeroth-order Hamiltonian and improves the shape of the potential energy surface significantly. We conclude by comparing our results of the dissocation energy and vibrational spectrum to those obtained from several highly accurate multiconfigurational methods and experiment. For a meaningful comparison, we used the extrapolation to the complete basis set for all methods involved.

• Author: Steven Vancoillie; Per-Åke Malmqvist; Valera Veryazov
• Department/s: Computational Chemistry
• Publishing year: 2016-02-01
• Language: English
• Pages: 1647-1655
• Publication/Series: Journal of Chemical Theory and Computation
• Volume: 12
• Issue: 4
• Links: http://dx.doi.org/10.1021/acs.jctc.6b00034
• Document type: Journal article
• Publisher: The American Chemical Society (ACS)
• Topic: Theoretical Chemistry (including Computational Chemistry)
• Status: Published
• ISBN/ISSN/Other: ISSN: 1549-9618