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

Vancoillie, Steven LU ; Malmqvist, Per-Åke LU and Veryazov, Valera LU (2016) In Journal of Chemical Theory and Computation 12(4). p.1647-1655
Abstract
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... (More)
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. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
Journal of Chemical Theory and Computation
volume
12
issue
4
pages
1647 - 1655
publisher
The American Chemical Society
external identifiers
  • pmid:26930185
  • wos:000374196400023
  • scopus:84964689464
ISSN
1549-9618
DOI
10.1021/acs.jctc.6b00034
language
English
LU publication?
yes
id
2adf7526-d239-4c3a-91bc-8847601b9262 (old id 8856716)
date added to LUP
2016-03-22 14:42:47
date last changed
2017-07-30 03:16:29
@article{2adf7526-d239-4c3a-91bc-8847601b9262,
  abstract     = {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       = {Vancoillie, Steven and Malmqvist, Per-Åke and Veryazov, Valera},
  issn         = {1549-9618},
  language     = {eng},
  month        = {02},
  number       = {4},
  pages        = {1647--1655},
  publisher    = {The American Chemical Society},
  series       = {Journal of Chemical Theory and Computation},
  title        = {Potential Energy Surface of the Chromium Dimer Re-re-revisited with Multiconfigurational Perturbation Theory.},
  url          = {http://dx.doi.org/10.1021/acs.jctc.6b00034},
  volume       = {12},
  year         = {2016},
}