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A matrix completion algorithm for efficient calculation of quantum and variational effects in chemical reactions

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/5.0091155· OSTI ID:1865680
 [1];  [2];  [2];  [2];  [2];  [2]
  1. Univ. of Southern California, Los Angeles, CA (United States); University of Southern California
  2. Univ. of Southern California, Los Angeles, CA (United States)
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This work examines the viability of matrix completion methods as cost-effective alternatives to full nuclear Hessians for calculating quantum and variational effects in chemical reactions. The harmonic variety-based matrix completion (HVMC) algorithm, developed in a previous study (https://doi.org/10.1063/5.0018326), exploits the low-rank character of the polynomial expansion of potential energy to recover, using a small sample, vibrational frequencies (square roots of nuclear Hessian eigenvalues) constituting the reaction path. Furthermore, these frequencies are essential for calculating rate coefficients using variational transition state theory with multidimensional tunneling (VTST-MT). HVMC performance is examined for four SN2 reactions and five hydrogen transfer reactions, with each H-transfer reaction consisting of at least one vibrational mode strongly coupled to the reaction coordinate. HVMC is robust and captures zero-point energies, vibrational free energies, zero-curvature tunneling, and adiabatic ground state and free energy barriers as well as their positions on the reaction coordinate. For medium to large reactions involving H-transfer, with the exception of the most complex Ir catalysis system, less than 35% of total eigenvalue information is necessary for accurate recovery of key VTST-MT observables.
Research Organization:
Univ. of Southern California, Los Angeles, CA (United States)
Sponsoring Organization:
USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0021417
OSTI ID:
1865680
Alternate ID(s):
OSTI ID: 1867933
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 18 Vol. 156; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

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