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Smolyak Algorithm Adapted to a System-Bath Separation: Application to an Encapsulated Molecule with Large-Amplitude Motions

Lauvergnat, David; Chen, Ahai; Benoit, David M.; Scribano, Yohann; Nauts, André; DavidLauvergnat

Authors

David Lauvergnat

Ahai Chen

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Dr David Benoit D.Benoit@hull.ac.uk
Senior Lecturer in Molecular Physics and Astrochemistry

Yohann Scribano

André Nauts

DavidLauvergnat



Abstract

A Smolyak algorithm adapted to system-bath separation is proposed for rigorous quantum simulations. This technique combines a sparse grid method with the system-bath concept in a specific configuration without limitations on the form of the Hamiltonian, thus achieving a highly efficient convergence of the excitation transitions for the "system"part. Our approach provides a general way to overcome the perennial convergence problem for the standard Smolyak algorithm and enables the simulation of floppy molecules with more than a hundred degrees of freedom. The efficiency of the present method is illustrated on the simulation of H2 caged in an sII clathrate hydrate including two kinds of cage modes. The transition energies are converged by increasing the number of normal modes of water molecules. Our results confirm the triplet splittings of both translational and rotational (j = 1) transitions of the H2 molecule. Furthermore, they show a slight increase of the translational transitions with respect to the ones in a rigid cage.

Citation

Lauvergnat, D., Chen, A., Benoit, D. M., Scribano, Y., Nauts, A., & DavidLauvergnat. (2022). Smolyak Algorithm Adapted to a System-Bath Separation: Application to an Encapsulated Molecule with Large-Amplitude Motions. Journal of chemical theory and computation : JCTC, https://doi.org/10.1021/acs.jctc.2c00108

Journal Article Type Article
Acceptance Date Apr 25, 2022
Online Publication Date May 18, 2022
Publication Date Jan 1, 2022
Deposit Date Jun 8, 2022
Publicly Available Date Jan 2, 2023
Journal Journal of Chemical Theory and Computation
Print ISSN 1549-9618
Electronic ISSN 1549-9626
Publisher American Chemical Society
Peer Reviewed Peer Reviewed
DOI https://doi.org/10.1021/acs.jctc.2c00108
Keywords Algorithms; Basis sets; Energy; Molecules; Solvates
Public URL https://hull-repository.worktribe.com/output/3999452