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The Chromium Dimer: Closing a Chapter of Quantum Chemistry

Larsson, Henrik R. and Zhai, Huanchen and Umrigar, C. J. and Chan, Garnet Kin-Lic (2022) The Chromium Dimer: Closing a Chapter of Quantum Chemistry. Journal of the American Chemical Society, 144 (35). pp. 15932-15937. ISSN 0002-7863. doi:10.1021/jacs.2c06357.

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The complex electronic structure and unusual potential energy curve of the chromium dimer have fascinated scientists for decades, with agreement between theory and experiment so far elusive. Here, we present a new ab initio simulation of the potential energy curve and vibrational spectrum that significantly improves on all earlier estimates. Our data support a shift in earlier experimental assignments of a cluster of vibrational frequencies by one quantum number. The new vibrational assignment yields an experimentally derived potential energy curve in quantitative agreement with theory across all bond lengths and across all measured frequencies. By solving this long-standing problem, our results raise the possibility of quantitative quantum chemical modeling of transition metal clusters with spectroscopic accuracy.

Item Type:Article
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URLURL TypeDescription ItemDiscussion Paper
Larsson, Henrik R.0000-0002-9417-1518
Zhai, Huanchen0000-0003-0086-0388
Chan, Garnet Kin-Lic0000-0001-8009-6038
Additional Information:We thank Doreen Leopold and Alec Wodtke for helpful discussions. Work by G.K.C. was supported by the US National Science Foundation (NSF) via grant no. CHE2102505. G.K.C. acknowledges additional support from the Simons Foundation via the Many-Electron Collaboration and the Investigator Award. Work by H.R.L., H.Z., and C.J.U. was supported by the Air Force Office of Scientific Research, under Award FA9550-18-1-0095. H.R.L. acknowledges support from a postdoctoral fellowship from the German Research Foundation (DFG) via grant LA 4442/1-1 during the first part of this work. Some of the computations were conducted at the Resnick High Performance Computing Center, a facility supported by the Resnick Sustainability Institute at the California Institute of Technology. The SHCI calculations were performed on the Bridges computer at the Pittsburgh Supercomputing Center under grant PHY170037.
Group:Resnick Sustainability Institute
Funding AgencyGrant Number
Simons FoundationUNSPECIFIED
Air Force Office of Scientific Research (AFOSR)FA9550-18-1-0095
Deutsche Forschungsgemeinschaft (DFG)LA 4442/1-1
Resnick Sustainability InstituteUNSPECIFIED
Issue or Number:35
Record Number:CaltechAUTHORS:20220908-232209149
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:116716
Deposited By: Olivia Warschaw
Deposited On:08 Sep 2022 23:26
Last Modified:08 Sep 2022 23:26

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