Vibrational heat-bath configuration interaction
- 16 February 2021
- journal article
- research article
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 154 (7), 074104
- https://doi.org/10.1063/5.0035454
Abstract
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.Keywords
Funding Information
- National Science Foundation (DGE-1644869)
- National Institutes of Health (1G20RR030893-01)
This publication has 54 references indexed in Scilit:
- Vibrational self-consistent field calculations for spectroscopy of biological molecules: new algorithmic developments and applicationsPhysical Chemistry Chemical Physics, 2013
- Iterative active-space selection for vibrational configuration interaction calculations using a reduced-coupling VSCF basisChemical Physics Letters, 2008
- Anharmonic Force Fields of Naphthalene-h 8 and Naphthalene-d 8The Journal of Physical Chemistry A, 2007
- Calculations of Vibrational Energy Levels by Using a Hybrid ab Initio and DFT Quartic Force Field: Application to AcetonitrileThe Journal of Physical Chemistry A, 2005
- MULTIMODE: A code to calculate rovibrational energies of polyatomic moleculesInternational Reviews in Physical Chemistry, 2003
- Calculation of anharmonic vibrational spectroscopy of small biological moleculesPhysChemComm, 2002
- Ab initio calculation of anharmonic vibrational states of polyatomic systems: Electronic structure combined with vibrational self-consistent fieldThe Journal of Chemical Physics, 1999
- Low-Energy Structures and Vibrational Frequencies of the Water Hexamer: Comparison with Benzene-(H2O)6Journal of the American Chemical Society, 1994
- Theoretical Methods for Rovibrational States of Floppy MoleculesAnnual Review of Physical Chemistry, 1989
- Application of SCF-SI theory to vibrational motion in polyatomic moleculesThe Journal of Physical Chemistry, 1979