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Title: A deterministic alternative to the full configuration interaction quantum Monte Carlo method

Abstract

Development of exponentially scaling methods has seen great progress in tackling larger systems than previously thought possible. One such approach, full configuration interaction quantum Monte Carlo, is a useful algorithm that allows exact diagonalization through stochastically sampling determinants. The method derives its utility from the information in the matrix elements of the Hamiltonian, along with a stochastic projected wave function, to find the important parts of Hilbert space. Yet, the stochastic representation of the wave function is not required to search Hilbert space efficiently, and here we describe a highly efficient deterministic method that can achieve chemical accuracy for a wide range of systems, including the difficult Cr2 molecule. We demonstrate for systems like Cr2 that such calculations can be performed in just a few cpu hours which makes it one of the most efficient and accurate methods that can attain chemical accuracy for strongly correlated systems. Furthermore, our method also allows efficient calculation of excited state energies, which we illustrate with benchmark results for the excited states of C2.

Authors:
 [1];  [1]; ORCiD logo [1];  [1];  [1]
  1. Univ. of California, Berkeley, CA (United States)
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF)
Sponsoring Org.:
USDOE Office of Science (SC), Advanced Scientific Computing Research (ASCR). Scientific Discovery through Advanced Computing (SciDAC); National Science Foundation (NSF)
OSTI Identifier:
1565479
Alternate Identifier(s):
OSTI ID: 1279018
Grant/Contract Number:  
AC05-00OR22725; SciDac
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 145; Journal Issue: 4; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Tubman, Norm M., Lee, Joonho, Takeshita, Tyler Y., Head-Gordon, Martin, and Whaley, K. Birgitta. A deterministic alternative to the full configuration interaction quantum Monte Carlo method. United States: N. p., 2016. Web. doi:10.1063/1.4955109.
Tubman, Norm M., Lee, Joonho, Takeshita, Tyler Y., Head-Gordon, Martin, & Whaley, K. Birgitta. A deterministic alternative to the full configuration interaction quantum Monte Carlo method. United States. https://doi.org/10.1063/1.4955109
Tubman, Norm M., Lee, Joonho, Takeshita, Tyler Y., Head-Gordon, Martin, and Whaley, K. Birgitta. 2016. "A deterministic alternative to the full configuration interaction quantum Monte Carlo method". United States. https://doi.org/10.1063/1.4955109. https://www.osti.gov/servlets/purl/1565479.
@article{osti_1565479,
title = {A deterministic alternative to the full configuration interaction quantum Monte Carlo method},
author = {Tubman, Norm M. and Lee, Joonho and Takeshita, Tyler Y. and Head-Gordon, Martin and Whaley, K. Birgitta},
abstractNote = {Development of exponentially scaling methods has seen great progress in tackling larger systems than previously thought possible. One such approach, full configuration interaction quantum Monte Carlo, is a useful algorithm that allows exact diagonalization through stochastically sampling determinants. The method derives its utility from the information in the matrix elements of the Hamiltonian, along with a stochastic projected wave function, to find the important parts of Hilbert space. Yet, the stochastic representation of the wave function is not required to search Hilbert space efficiently, and here we describe a highly efficient deterministic method that can achieve chemical accuracy for a wide range of systems, including the difficult Cr2 molecule. We demonstrate for systems like Cr2 that such calculations can be performed in just a few cpu hours which makes it one of the most efficient and accurate methods that can attain chemical accuracy for strongly correlated systems. Furthermore, our method also allows efficient calculation of excited state energies, which we illustrate with benchmark results for the excited states of C2.},
doi = {10.1063/1.4955109},
url = {https://www.osti.gov/biblio/1565479}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 4,
volume = 145,
place = {United States},
year = {Fri Jul 29 00:00:00 EDT 2016},
month = {Fri Jul 29 00:00:00 EDT 2016}
}

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Works referenced in this record:

Using perturbatively selected configuration interaction in quantum Monte Carlo calculations
journal, September 2013


Highly correlated calculations with a polynomial cost algorithm: A study of the density matrix renormalization group
journal, March 2002


Communication: An adaptive configuration interaction approach for strongly correlated electrons with tunable accuracy
journal, April 2016


Semistochastic Projector Monte Carlo Method
journal, December 2012


Selected versus complete configuration interaction expansions
journal, August 1991


The Configuration Interaction Method: Advances in Highly Correlated Approaches
book, January 1999


Investigation of the full configuration interaction quantum Monte Carlo method using homogeneous electron gas models
journal, June 2012


The radical character of the acenes: A density matrix renormalization group study
journal, October 2007


Fixed-node diffusion Monte Carlo potential energy curve of the fluorine molecule F 2 using selected configuration interaction trial wavefunctions
journal, January 2015


A configuration interaction study of the spin dipole-dipole parameters for formaldehyde and methylene
journal, September 1973


An excited-state approach within full configuration interaction quantum Monte Carlo
journal, October 2015


Adaptive multiconfigurational wave functions
journal, March 2014


The density-matrix renormalization group
journal, April 2005


The radical character of the acenes: A density matrix renormalization group study
text, January 2007


Taming the First-Row Diatomics: A Full Configuration Interaction Quantum Monte Carlo Study
journal, October 2012


Communications: Survival of the fittest: Accelerating convergence in full configuration-interaction quantum Monte Carlo
journal, January 2010


Efficient Heat-Bath Sampling in Fock Space
journal, March 2016


Improved implementation and application of the individually selecting configuration interaction method
journal, January 2005


Low-energy spectrum of iron–sulfur clusters directly from many-particle quantum mechanics
journal, August 2014


Towards an exact description of electronic wavefunctions in real solids
journal, December 2012


Convergence of an improved CIPSI algorithm
journal, February 1983


More π Electrons Make a Difference: Emergence of Many Radicals on Graphene Nanoribbons Studied by Ab Initio DMRG Theory
journal, December 2012


Size‐consistent self‐consistent truncated or selected configuration interaction
journal, July 1993


Approximating full configuration interaction with selected configuration interaction and perturbation theory
journal, April 1991


Full Configuration Interaction Excitations of Ethene and Butadiene: Resolution of an Ancient Question
journal, September 2012


Studying Two-Dimensional Systems with the Density Matrix Renormalization Group
journal, March 2012


The ORCA program system: The ORCA program system
journal, June 2011


The effect of quantization on the full configuration interaction quantum Monte Carlo sign problem
journal, January 2013


Communication: Excited states, dynamic correlation functions and spectral properties from full configuration interaction quantum Monte Carlo
journal, November 2012


Estimating full configuration interaction limits from a Monte Carlo selection of the expansion space
journal, August 1995


Density-matrix algorithms for quantum renormalization groups
journal, October 1993


Multiconfiguration Self-Consistent Field and Multireference Configuration Interaction Methods and Applications
journal, December 2011


Ab initio quantum chemistry using the density matrix renormalization group
journal, March 1999


The lowest energy states of the group-IIIA–group-VA heteronuclear diatomics: BN, BP, AlN, and AlP from full configuration interaction calculations
journal, September 2006


Recent advances in multireference second order perturbation CI: The CIPSI method revisited
journal, January 1987


Communication: Toward an improved control of the fixed-node error in quantum Monte Carlo: The case of the water molecule
journal, April 2016


Psi4: an open-source ab initio electronic structure program : Psi4: an electronic structure program
journal, October 2011

  • Turney, Justin M.; Simmonett, Andrew C.; Parrish, Robert M.
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 4
  • https://doi.org/10.1002/wcms.93

Fully optimized contracted Gaussian basis sets for atoms Li to Kr
journal, August 1992


Surprising cases of divergent behavior in Mo/ller–Plesset perturbation theory
journal, September 1996


Configuration interaction singles natural orbitals: An orbital basis for an efficient and size intensive multireference description of electronic excited states
journal, January 2015


A spectroscopy oriented configuration interaction procedure
journal, November 2003


Open-Source Development Experiences in Scientific Software: The HANDE Quantum Monte Carlo Project
journal, November 2015


Fermion Monte Carlo without fixed nodes: A game of life, death, and annihilation in Slater determinant space
journal, January 2009


The ab-initio density matrix renormalization group in practice
journal, January 2015


Development of Monte Carlo configuration interaction: Natural orbitals and second-order perturbation theory
journal, November 2012


Direct selected multireference configuration interaction calculations for large systems using localized orbitals
journal, July 2011


Iterative perturbation calculations of ground and excited state energies from multiconfigurational zeroth‐order wavefunctions
journal, June 1973


Is Mo/ller–Plesset perturbation theory a convergent ab initio method?
journal, June 2000


Breaking the carbon dimer: The challenges of multiple bond dissociation with full configuration interaction quantum Monte Carlo methods
journal, August 2011


iCI: Iterative CI toward full CI
journal, January 2016


Analytic nuclear forces and molecular properties from full configuration interaction quantum Monte Carlo
journal, August 2015


Works referencing / citing this record:

Efficient hybridization fitting for dynamical mean-field theory via semi-definite relaxation
text, January 2019


The density matrix renormalization group in chemistry and molecular physics: Recent developments and new challenges
journal, January 2020


Iterative submatrix diagonalisation for large configuration interaction problems
journal, September 2017


Stochastic perturbation theory in a limited configuration space
journal, September 2019


autoCAS : A Program for Fully Automated Multiconfigurational Calculations
journal, June 2019


Time dependent adaptive configuration interaction applied to attosecond charge migration
journal, November 2019


Perspective: Multireference coupled cluster theories of dynamical electron correlation
journal, July 2018


From Real Materials to Model Hamiltonians With Density Matrix Downfolding
journal, May 2018


Selected configuration interaction dressed by perturbation
journal, August 2018


Unbiasing the initiator approximation in full configuration interaction quantum Monte Carlo.
text, January 2019


Communication: Approaching exact quantum chemistry by cluster analysis of full configuration interaction quantum Monte Carlo wave functions
journal, October 2018


Evaluation of full valence correlation energies and gradients
journal, June 2019


QMCPACK : an open source ab initio quantum Monte Carlo package for the electronic structure of atoms, molecules and solids
journal, April 2018


Reduced scaling Hilbert space variational Monte Carlo
journal, November 2018


Ab initio computations of molecular systems by the auxiliary-field quantum Monte Carlo method
journal, May 2018


Accurate excited-state energetics by a combination of Monte Carlo sampling and equation-of-motion coupled-cluster computations
journal, March 2019


Unbiasing the initiator approximation in full configuration interaction quantum Monte Carlo
journal, December 2019


Excitation variance matching with limited configuration interaction expansions in variational Monte Carlo
journal, October 2017


Quantum computational chemistry
text, January 2018


A systematic construction of configuration interaction wavefunctions in the complete CI space
journal, October 2019


Vibrational adaptive sampling configuration interaction
journal, October 2019


From real materials to model Hamiltonians with density matrix downfolding
text, January 2017


Quantum Chemistry in the Age of Quantum Computing
journal, August 2019


Machine Learning Configuration Interaction
journal, October 2018


Machine Learning Configuration Interaction for ab Initio Potential Energy Curves
journal, October 2019


A Multireference Quantum Krylov Algorithm for Strongly Correlated Electrons
journal, February 2020


High Accuracy ab Initio Calculations of Rotational–Vibrational Levels of the HCN/HNC System
journal, January 2018


The Shape of Full Configuration Interaction to Come
journal, December 2020