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Title: 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:
ORCiD logo [1];  [2];  [2]
  1. College of William and Mary, Williamsburg, VA (United States); Old Dominion Univ., Norfolk, VA (United States)
  2. College of William and Mary, Williamsburg, VA (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (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. doi:10.1063/1.4954245.
Purwanto, Wirawan, Zhang, Shiwei, and Krakauer, Henry. Mon . "Auxiliary-field quantum Monte Carlo calculations of the molybdenum dimer". United States. doi: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 = {2016},
month = {6}
}

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