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Fast and Accurate Computation of Nonadiabatic Coupling Matrix Elements Using the Truncated Leibniz Formula and Mixed-Reference Spin-Flip Time-Dependent Density Functional Theory

Lee, Seunghoon and Horbatenko, Yevhen and Filatov, Michael and Choi, Cheol Ho (2021) Fast and Accurate Computation of Nonadiabatic Coupling Matrix Elements Using the Truncated Leibniz Formula and Mixed-Reference Spin-Flip Time-Dependent Density Functional Theory. Journal of Physical Chemistry Letters, 12 (19). pp. 4722-4728. ISSN 1948-7185. https://resolver.caltech.edu/CaltechAUTHORS:20210513-144618100

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Abstract

We present a fast and accurate numerical algorithm for computing the first-order nonadiabatic coupling matrix element (NACME). The algorithm employs the truncated Leibniz formula (TLF) approximation within the finite-difference method, which makes it easily applicable in connection with any wave function-based methodology. In this work, we used the algorithm in connection with the recently developed mixed-reference spin-flip time-dependent density functional theory (MRSF-TDDFT, MRSF for brevity). The accuracy is assessed for NACME between the singlet electronic states of a dissociating hydrogen molecule. It is demonstrated that an intermediate approximation, TLF(1), affords a negligible numeric error on the order of ∼10⁻¹⁰ a.u. while enabling a fast computation of NACME. As the MRSF method yields the correct description of the dissociation curves of H₂ for all the electronic states involved, the numeric TLF(1)/MRSF NACME values are in excellent agreement with the reference analytical values obtained by the full configuration interaction. For polyatomic molecules, the MRSF NAC vectors agree very closely with the MRCISD NAC vectors. Hence, the proposed protocol is a promising tool for the evaluation of NACMEs.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/acs.jpclett.1c00932DOIArticle
ORCID:
AuthorORCID
Lee, Seunghoon0000-0003-3665-587X
Horbatenko, Yevhen0000-0002-6913-9241
Filatov, Michael0000-0002-1541-739X
Choi, Cheol Ho0000-0002-8757-1396
Additional Information:© 2021 American Chemical Society. Received: March 23, 2021; Accepted: May 7, 2021; Published: May 13, 2021. This work was supported by the Samsung Science and Technology Foundations Grant SSTF-BA1701-12 (to C.H.C.) for fundamental theory developments and the NRF grants 2019H1D3A2A02102948 (to M.F.) and 2020R1A2C2008246 and 2020R1A5A1019141 (to C.H.C.) funded by the Ministry of Science and ICT for applications of the developed methodologies. S.L. was supported by the US National Science Foundation via Award CHE-1655333. The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
Samsung Science and Technology FoundationSSTF-BA1701-12
National Research Foundation of Korea2019H1D3A2A02102948
National Research Foundation of Korea2020R1A2C2008246
National Research Foundation of Korea2020R1A5A1019141
NSFCHE-1655333
Subject Keywords:Algorithms, Dissociation, Approximation, Mathematical methods, Molecules
Issue or Number:19
Record Number:CaltechAUTHORS:20210513-144618100
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20210513-144618100
Official Citation:Fast and Accurate Computation of Nonadiabatic Coupling Matrix Elements Using the Truncated Leibniz Formula and Mixed-Reference Spin-Flip Time-Dependent Density Functional Theory. Seunghoon Lee, Yevhen Horbatenko, Michael Filatov, and Cheol Ho Choi. The Journal of Physical Chemistry Letters 2021 12 (19), 4722-4728; DOI: 10.1021/acs.jpclett.1c00932
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:109124
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:14 May 2021 14:10
Last Modified:27 May 2021 17:01

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