Communication: Calculation of interatomic forces and optimization of molecular geometry with auxiliary-field quantum Monte Carlo

Motta, Mario; Zhang, Shiwei

doi:10.1063/1.5029508

Title: Communication: Calculation of interatomic forces and optimization of molecular geometry with auxiliary-field quantum Monte Carlo

Journal Article · Tue May 08 00:00:00 EDT 2018 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.5029508· OSTI ID:1540205

^[1]; Zhang, Shiwei ^[2]

California Inst. of Technology (CalTech), Pasadena, CA (United States)
College of William and Mary, Williamsburg, VA (United States)

We introduce an algorithm for accurate, systematic, and scalable computation of interatomic forces within the auxiliary-field quantum Monte Carlo (AFQMC) method. The algorithm relies on the Hellmann-Feynman theorem and incorporates Pulay corrections in the presence of atomic orbital basis sets. We benchmark the technique for small molecules by comparing the computed forces with the derivatives of the AFQMC potential energy surface and by direct comparison with other quantum chemistry methods. Furthermore, we perform geometry optimizations using the steepest descent algorithm in larger molecules. With realistic basis sets, we obtain equilibrium geometries in agreement, within statistical error bars, with experimental values. The increase in computational cost for computing forces in this approach is only a small prefactor over that of calculating the total energy. This paves the way for a general and efficient method for geometry optimization and molecular dynamics within AFQMC.

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Research Organization:: College of William and Mary, Williamsburg, VA (United States)

Sponsoring Organization:: USDOE Office of Science (SC); National Science Foundation (NSF)

Grant/Contract Number:: SC0001303; Grant no. DE-SC0001303

OSTI ID:: 1540205

Alternate ID(s):: OSTI ID: 1436372

Journal Information:: Journal of Chemical Physics, Vol. 148, Issue 18; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 19 works

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Gaussian process based optimization of molecular geometries using statistically sampled energy surfaces from quantum Monte Carlo Archibald, R.; Krogel, J. T.; Kent, P. R. C. The Journal of Chemical Physics, Vol. 149, Issue 16 https://doi.org/10.1063/1.5040584	journal	October 2018
Auxiliary-field quantum Monte Carlo calculations of the structural properties of nickel oxide Zhang, Shuai; Malone, Fionn D.; Morales, Miguel A. The Journal of Chemical Physics, Vol. 149, Issue 16 https://doi.org/10.1063/1.5040900	journal	October 2018
Non-orthogonal multi-Slater determinant expansions in auxiliary field quantum Monte Carlo Landinez Borda, Edgar Josué; Gomez, John; Morales, Miguel A. The Journal of Chemical Physics, Vol. 150, Issue 7 https://doi.org/10.1063/1.5049143	journal	February 2019
An auxiliary-Field quantum Monte Carlo perspective on the ground state of the dense uniform electron gas: An investigation with Hartree-Fock trial wavefunctions Lee, Joonho; Malone, Fionn D.; Morales, Miguel A. The Journal of Chemical Physics, Vol. 151, Issue 6 https://doi.org/10.1063/1.5109572	journal	August 2019
Calculating ground-state properties of correlated fermionic systems with BCS trial wave functions in Slater determinant path-integral approaches Vitali, Ettore; Rosenberg, Peter; Zhang, Shiwei Physical Review A, Vol. 100, Issue 2 https://doi.org/10.1103/physreva.100.023621	journal	August 2019
Hamiltonian symmetries in auxiliary-field quantum Monte Carlo calculations for electronic structure Motta, Mario; Zhang, Shiwei; Chan, Garnet Kin-Lic Physical Review B, Vol. 100, Issue 4 https://doi.org/10.1103/physrevb.100.045127	journal	July 2019
Non-Orthogonal Multi-Slater Determinant Expansions in Auxiliary Field Quantum Monte Carlo Borda, Edgar Josué Landinez; Gomez, John A.; Morales, Miguel A. arXiv https://doi.org/10.48550/arxiv.1801.10307	preprint	January 2018
Calculating ground state properties of correlated fermionic systems with BCS trial wave functions in Slater determinant path-integral approaches Vitali, Ettore; Rosenberg, Peter; Zhang, Shiwei arXiv https://doi.org/10.48550/arxiv.1905.05012	text	January 2019

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