Auxiliary-field quantum Monte Carlo calculations of the molybdenum dimer
Abstract
Chemical accuracy is difficult to achieve for systems with transition metal atoms. Third row transition metal atoms are particularly challenging due to strong electron-electron correlation in localized d-orbitals. The Cr2 molecule is an outstanding example, which we previously treated with highly accurate auxiliary-field quantum Monte Carlo (AFQMC) calculations. Somewhat surprisingly, computational description of the isoelectronic Mo2 dimer has also, to date, been scattered and less than satisfactory. We present high-level theoretical benchmarks of the Mo2 singlet ground state (X1Σ+g) and first triplet excited state (a3Σ+u), using the phaseless AFQMC calculations. Extrapolation to the complete basis set limit is performed. Furthermore, excellent agreement with experimental spectroscopic constants is obtained. We also present a comparison of the correlation effects in Cr2 and Mo2.
- Authors:
-
- College of William and Mary, Williamsburg, VA (United States); Old Dominion Univ., Norfolk, VA (United States)
- College of William and Mary, Williamsburg, VA (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF); UT-Battelle LLC, Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC)
- OSTI Identifier:
- 1467572
- Alternate Identifier(s):
- OSTI ID: 1259372
- Grant/Contract Number:
- AC05-00OR22725; FG02-09ER16046; FG02-11ER16257
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Chemical Physics
- Additional Journal Information:
- Journal Volume: 144; Journal Issue: 24; Journal ID: ISSN 0021-9606
- Publisher:
- American Institute of Physics (AIP)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Purwanto, Wirawan, Zhang, Shiwei, and Krakauer, Henry. Auxiliary-field quantum Monte Carlo calculations of the molybdenum dimer. United States: N. p., 2016.
Web. doi:10.1063/1.4954245.
Purwanto, Wirawan, Zhang, Shiwei, & Krakauer, Henry. Auxiliary-field quantum Monte Carlo calculations of the molybdenum dimer. United States. https://doi.org/10.1063/1.4954245
Purwanto, Wirawan, Zhang, Shiwei, and Krakauer, Henry. Mon .
"Auxiliary-field quantum Monte Carlo calculations of the molybdenum dimer". United States. https://doi.org/10.1063/1.4954245. https://www.osti.gov/servlets/purl/1467572.
@article{osti_1467572,
title = {Auxiliary-field quantum Monte Carlo calculations of the molybdenum dimer},
author = {Purwanto, Wirawan and Zhang, Shiwei and Krakauer, Henry},
abstractNote = {Chemical accuracy is difficult to achieve for systems with transition metal atoms. Third row transition metal atoms are particularly challenging due to strong electron-electron correlation in localized d-orbitals. The Cr2 molecule is an outstanding example, which we previously treated with highly accurate auxiliary-field quantum Monte Carlo (AFQMC) calculations. Somewhat surprisingly, computational description of the isoelectronic Mo2 dimer has also, to date, been scattered and less than satisfactory. We present high-level theoretical benchmarks of the Mo2 singlet ground state (X1Σ+g) and first triplet excited state (a3Σ+u), using the phaseless AFQMC calculations. Extrapolation to the complete basis set limit is performed. Furthermore, excellent agreement with experimental spectroscopic constants is obtained. We also present a comparison of the correlation effects in Cr2 and Mo2.},
doi = {10.1063/1.4954245},
journal = {Journal of Chemical Physics},
number = 24,
volume = 144,
place = {United States},
year = {Mon Jun 27 00:00:00 EDT 2016},
month = {Mon Jun 27 00:00:00 EDT 2016}
}
Web of Science
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