Vibrational Heat-Bath Configuration Interaction

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 to 48 degrees of freedom and use anharmonic potential energy surfaces truncated at fourth and sixth order. For all molecules studied, VHCI produces vibrational spectra of tens or hundreds of states with sub-wavenumber accuracy at low computational cost.

References in corpus (12)

• Heat-bath Configuration Interaction: An efficient selected CI algorithm inspired by heat-bath sampling
• Semistochastic Heat-bath Configuration Interaction method: selected configuration interaction with semistochastic perturbation theory
• A deterministic alternative to the full configuration interaction quantum Monte Carlo method
• An adaptive configuration interaction approach for strongly correlated electrons with tunable accuracy
• Modern Approaches to Exact Diagonalization and Selected Configuration Interaction with the Adaptive Sampling CI Method
• The Ground State Electronic Energy of Benzene
• Excited states using semistochastic heat-bath configuration interaction
• Fast Semistochastic Heat-Bath Configuration Interaction
• Direct comparison of many-body methods for realistic electronic Hamiltonians
• Calculating vibrational spectra with sum of product basis functions without storing full-dimensional vectors or matrices
• Vibrational Density Matrix Renormalization Group
• Almost exact energies for the Gaussian-2 set with the semistochastic heat-bath configuration interaction method

Cited by in corpus (5)

• Excited-state DMRG made simple with FEAST
• Multicomponent Heat-Bath Configuration Interaction with the Perturbative Correction for the Calculation of Protonic Excited States
• Computing vibrational energy levels by solving linear equations using a tensor method with an imposed rank
• Benchmarking vibrational spectra: 5000 accurate eigenstates of acetonitrile using tree tensor network states
• Rovibrational energy levels of H${}_2$O by quantum computing