CaltechAUTHORS
  A Caltech Library Service

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

Motta, Mario and Zhang, Shiwei (2018) Calculation of interatomic forces and optimization of molecular geometry with auxiliary-field quantum Monte Carlo. Journal of Chemical Physics, 148 (18). Art. No. 181101. ISSN 0021-9606. https://resolver.caltech.edu/CaltechAUTHORS:20180508-095250649

[img] PDF - Published Version
See Usage Policy.

859Kb
[img] PDF - Submitted Version
See Usage Policy.

3778Kb
[img] PDF - Supplemental Material
See Usage Policy.

177Kb

Use this Persistent URL to link to this item: https://resolver.caltech.edu/CaltechAUTHORS:20180508-095250649

Abstract

We propose 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 method 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. We then 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 approach for geometry optimization and molecular dynamics within AFQMC.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1063/1.5029508DOIArticle
https://arxiv.org/abs/1803.05599arXivDiscussion Paper
ORCID:
AuthorORCID
Motta, Mario0000-0003-1647-9864
Additional Information:© 2018 Published by AIP Publishing. Received 15 March 2018; accepted 24 April 2018; published online 8 May 2018. We acknowledge support from NSF (Grant No. DMR-1409510), DOE (Grant No. DE-SC0001303), and the Simons Foundation. Computations were carried out at the Extreme Science and Engineering Discovery Environment (XSEDE), which is supported by the National Science Foundation Grant No. ACI-1053575, at the Storm and SciClone Clusters at the College of William and Mary. M.M. acknowledges James Shee and Qiming Sun for valuable interaction.
Funders:
Funding AgencyGrant Number
NSFDMR-1409510
Department of Energy (DOE)DE-SC0001303
Simons FoundationUNSPECIFIED
NSFACI-1053575
Issue or Number:18
Record Number:CaltechAUTHORS:20180508-095250649
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20180508-095250649
Official Citation:Communication: Calculation of interatomic forces and optimization of molecular geometry with auxiliary-field quantum Monte Carlo. Mario Motta and Shiwei Zhang. The Journal of Chemical Physics 2018 148:18
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:86276
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:08 May 2018 17:10
Last Modified:03 Oct 2019 19:41

Repository Staff Only: item control page