Potential Energy Surface of the Chromium Dimer Re-re-revisited with Multiconfigurational Perturbation Theory
(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)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/8856716
- author
- Vancoillie, Steven LU ; Malmqvist, Per-Åke LU and Veryazov, Valera LU
- organization
- publishing date
- 2016-02-01
- 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 (ACS)
- external identifiers
-
- pmid:26930185
- wos:000374196400023
- scopus:84964689464
- pmid:26930185
- 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
- 2016-04-01 10:32:19
- date last changed
- 2023-01-02 05:31:39
@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 (ACS)}}, 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}}, doi = {{10.1021/acs.jctc.6b00034}}, volume = {{12}}, year = {{2016}}, }