Saller, Maximilian A. C. and Habershon, Scott (2017) Quantum dynamics with short-time trajectories and minimal adaptive basis sets. Journal of Chemical Theory and Computation, 13 (7). pp. 3085-3096. doi:10.1021/acs.jctc.7b00021 ISSN 1549-9618.

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Abstract

Methods for solving the time-dependent Schrödinger equation via basis set expansion of the wave function can generally be categorized as having either static (time-independent) or dynamic (time-dependent) basis functions. We have recently introduced an alternative simulation approach which represents a middle road between these two extremes, employing dynamic (classical-like) trajectories to create a static basis set of Gaussian wavepackets in regions of phase-space relevant to future propagation of the wave function [J. Chem. Theory Comput., 11, 8 (2015)]. Here, we propose and test a modification of our methodology which aims to reduce the size of basis sets generated in our original scheme. In particular, we employ short-time classical trajectories to continuously generate new basis functions for short-time quantum propagation of the wave function; to avoid the continued growth of the basis set describing the time-dependent wave function, we employ Matching Pursuit to periodically minimize the number of basis functions required to accurately describe the wave function. Overall, this approach generates a basis set which is adapted to evolution of the wave function while also being as small as possible. In applications to challenging benchmark problems, namely a 4-dimensional model of photoexcited pyrazine and three different double-well tunnelling problems, we find that our new scheme enables accurate wave function propagation with basis sets which are around an order-of-magnitude smaller than our original trajectory-guided basis set methodology, highlighting the benefits of adaptive strategies for wave function propagation.

Item Type:	Journal Article
Subjects:	Q Science > QC Physics
Divisions:	Faculty of Science, Engineering and Medicine > Science > Chemistry Faculty of Science, Engineering and Medicine > Science > Centre for Scientific Computing
Library of Congress Subject Headings (LCSH):	Quantum theory, Schrödinger equation, Gaussian processes
Journal or Publication Title:	Journal of Chemical Theory and Computation
Publisher:	American Chemical Society
ISSN:	1549-9618
Official Date:	31 June 2017
Dates:	Date Event 31 June 2017 Published 31 May 2017 Available 31 May 2017 Accepted 10 January 2017 Submitted
Volume:	13
Number:	7
Page Range:	pp. 3085-3096
DOI:	10.1021/acs.jctc.7b00021
Status:	Peer Reviewed
Publication Status:	Published
Access rights to Published version:	Restricted or Subscription Access
Date of first compliant deposit:	4 December 2017
Date of first compliant Open Access:	31 May 2018
RIOXX Funder/Project Grant:	Project/Grant ID RIOXX Funder Name Funder ID UNSPECIFIED Engineering and Physical Sciences Research Council http://dx.doi.org/10.13039/501100000266
Related URLs:	Related dataset

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