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Methods to Calculate Electronic Excited-State Dynamics for Molecules on Large Metal Clusters with Many States: Ensuring Fast Overlap Calculations and a Robust Choice of Phase

Chen, Hsing-Ta and Chen, Junhan and Cofer-Shabica, D. Vale and Zhou, Zeyu and Athavale, Vishikh and Medders, Gregory and Menger, Maximilian F. S. J. and Subotnik, Joseph E. and Jin, Zuxin (2022) Methods to Calculate Electronic Excited-State Dynamics for Molecules on Large Metal Clusters with Many States: Ensuring Fast Overlap Calculations and a Robust Choice of Phase. Journal of Chemical Theory and Computation, 18 (6). pp. 3296-3307. ISSN 1549-9618. doi:10.1021/acs.jctc.1c01304. https://resolver.caltech.edu/CaltechAUTHORS:20220104-157981000

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Abstract

We present an efficient set of methods for propagating excited-state dynamics involving a large number of configuration interaction singles (CIS) or Tamm-Dancoff approximation (TDA) single-reference excited states. Specifically, (i) following Head-Gordon et al., we implement an exact evaluation of the overlap of singly-excited CIS/TDA electronic states at different nuclear geometries using a biorthogonal basis and (ii) we employ a unified protocol for choosing the correct phase for each adiabat at each geometry. For many-electron systems, the combination of these techniques significantly reduces the computational cost of integrating the electronic Schrodinger equation and imposes minimal overhead on top of the underlying electronic structure calculation. As a demonstration, we calculate the electronic excited-state dynamics for a hydrogen molecule scattering off a silver metal cluster, focusing on high-lying excited states, where many electrons can be excited collectively and crossings are plentiful. Interestingly, we find that the high-lying, plasmon-like collective excitation spectrum changes with nuclear dynamics, highlighting the need to simulate non-adiabatic nuclear dynamics and plasmonic excitations simultaneously. In the future, the combination of methods presented here should help theorists build a mechanistic understanding of plasmon-assisted charge transfer and excitation energy relaxation processes near a nanoparticle or metal surface.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/acs.jctc.1c01304DOIArticle
https://doi.org/10.26434/chemrxiv-2021-t433bDOIDiscussion Paper
ORCID:
AuthorORCID
Chen, Hsing-Ta0000-0002-6619-1861
Chen, Junhan0000-0003-4843-6324
Cofer-Shabica, D. Vale0000-0003-4623-6521
Zhou, Zeyu0000-0001-8681-9460
Athavale, Vishikh0000-0002-0571-2336
Medders, Gregory0000-0001-8988-4401
Menger, Maximilian F. S. J.0000-0003-1442-9601
Subotnik, Joseph E.0000-0003-2170-2020
Jin, Zuxin0000-0002-1533-3348
Additional Information:© 2022 American Chemical Society. Received: December 27, 2021; Published: May 24, 2022. We thank Christine Aikens for providing the tetrahedral geometries of the silver cluster. This work has been supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Award no. DE-SC0019397 (JES). It also used resources of the National Energy Research Scientific Computing Center (NERSC), a U.S. Department of Energy Office of Science User Facility operated under Contract no. DE-AC02-05CH11231. The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
Department of Energy (DOE)DE-SC0019397
Department of Energy (DOE)DE-AC02-05CH11231
Subject Keywords:Chemical calculations, Determinants, Mathematical methods, Phases of matter, Quantum mechanics
Issue or Number:6
DOI:10.1021/acs.jctc.1c01304
Record Number:CaltechAUTHORS:20220104-157981000
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20220104-157981000
Official Citation:Methods to Calculate Electronic Excited-State Dynamics for Molecules on Large Metal Clusters with Many States: Ensuring Fast Overlap Calculations and a Robust Choice of Phase. Hsing-Ta Chen, Junhan Chen, D. Vale Cofer-Shabica, Zeyu Zhou, Vishikh Athavale, Gregory Medders, Maximilian F. S. J. Menger, Joseph E. Subotnik, and Zuxin Jin. Journal of Chemical Theory and Computation 2022 18 (6), 3296-3307; DOI: 10.1021/acs.jctc.1c01304
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:112687
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:04 Jan 2022 22:02
Last Modified:30 Jun 2022 18:47

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