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Computation of molecular ionization energies using an ensemble density functional theory method

Filatov, Michael and Lee, Seunghoon and Choi, Cheol Ho (2020) Computation of molecular ionization energies using an ensemble density functional theory method. Journal of Chemical Theory and Computation, 16 (7). pp. 4489-4504. ISSN 1549-9618. https://resolver.caltech.edu/CaltechAUTHORS:20200518-131855368

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Abstract

Computation of the ionization energies and of the respective Dyson orbitals based on the use of the extended Koopmans theorem (EKT) is implemented in connection with an ensemble density functional theory (eDFT) method, the state-interaction state-averaged spin-restricted ensemble-referenced Kohn–Sham (SI-SA-REKS or SSR) method. The new methodology enables fast computation of the ionization energies and evaluation of the respective Dyson orbitals, the square norms of which are related with the ionization probabilities, in the ground and excited electronic states of molecules. As the application of EKT recycles the intermediate quantities from the SSR analytical energy gradient, evaluation of the ionization energies and probabilities can be carried out on-the-fly during the nonadiabatic molecular dynamics simulations. This opens up a perspective for fast theoretical simulation of the time-resolved photoelectron spectroscopy observations. In the present work, the new methodology is tested in the computation of the ionization energies and Dyson orbitals of several molecules in the ground and excited electronic states, including strongly correlated species, such as the ozone molecule, dissociating chemical bonds, and conical intersections.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/acs.jctc.0c00218DOIArticle
ORCID:
AuthorORCID
Filatov, Michael0000-0002-1541-739X
Choi, Cheol Ho0000-0002-8757-1396
Additional Information:© 2020 American Chemical Society. Received: March 4, 2020; Published: May 18, 2020. This work was supported by the National Research Foundation of Korea (NRF) Grant 2019H1D3A2A02102948. The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
National Research Foundation of Korea2019H1D3A2A02102948
Subject Keywords:Electronic properties, Molecules, Ionization, Energy, Mathematical methods
Issue or Number:7
Record Number:CaltechAUTHORS:20200518-131855368
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20200518-131855368
Official Citation:Computation of Molecular Ionization Energies Using an Ensemble Density Functional Theory Method. Michael Filatov, Seunghoon Lee, and Cheol Ho Choi. Journal of Chemical Theory and Computation 2020 16 (7), 4489-4504; DOI: 10.1021/acs.jctc.0c00218
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:103282
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:18 May 2020 20:31
Last Modified:15 Jul 2020 20:36

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