We introduce vibrational heat-bath configuration interaction (VHCI) as an accurate and efficient method for calculating vibrational eigenstates of anharmonic systems. Inspired by its origin in electronic structure theory, VHCI is a selected CI approach that uses a simple criterion to identify important basis states with a pre-sorted list of anharmonic force constants. Screened second-order perturbation theory and simple extrapolation techniques provide significant improvements to variational energy estimates. We benchmark VHCI on four molecules with 12–48 degrees of freedom and use anharmonic potential energy surfaces truncated at fourth and sixth orders. When compared to other methods using the same truncated potentials, VHCI produces vibrational spectra of tens or hundreds of states with sub-wavenumber accuracy at low computational cost.
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21 February 2021
Research Article|
February 16 2021
Vibrational heat-bath configuration interaction
Jonathan H. Fetherolf;
Jonathan H. Fetherolf
1
Department of Chemistry, Columbia University
, New York, New York 10027, USA
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Timothy C. Berkelbach
Timothy C. Berkelbach
a)
1
Department of Chemistry, Columbia University
, New York, New York 10027, USA
2
Center for Computational Quantum Physics, Flatiron Institute
, New York, New York 10010, USA
a)Author to whom correspondence should be addressed: [email protected]
Search for other works by this author on:
a)Author to whom correspondence should be addressed: [email protected]
J. Chem. Phys. 154, 074104 (2021)
Article history
Received:
October 28 2020
Accepted:
January 10 2021
Citation
Jonathan H. Fetherolf, Timothy C. Berkelbach; Vibrational heat-bath configuration interaction. J. Chem. Phys. 21 February 2021; 154 (7): 074104. https://doi.org/10.1063/5.0035454
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