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Mixed-Reference Spin-Flip Time-Dependent Density Functional Theory for Accurate X-ray Absorption Spectroscopy

Park, Woojin and Alías-Rodríguez, Marc and Cho, Daeheum and Lee, Seunghoon and Huix-Rotllant, Miquel and Choi, Cheol Ho (2022) Mixed-Reference Spin-Flip Time-Dependent Density Functional Theory for Accurate X-ray Absorption Spectroscopy. . (Unpublished) https://resolver.caltech.edu/CaltechAUTHORS:20220705-346766000

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Abstract

It is demonstrated that the challenging core hole-particle (CHP) orbital relaxation for core electron spectra can be readily achieved by the mixed-reference spin-flip (MRSF)-TDDFT. With the additional scalar relativistic effects on K-edge excitation energies of 24 second- and 17 third-row molecules, the particular ∆CHP-MRSF(R) exhibited near perfect predictions with RMSE ∼ 0.5 eV, featuring a median value of 0.3 and and an interquartile range of 0.4. Overall, the CHP effect is 2 ∼ 4 times stronger than relativistic ones, contributing more than 20 eV in the cases of sulfur and chlorine third-row atoms. Such high precision allows to explain the splitting and spectral shapes of O, N and C atom K-edges in the ground state of thymine with atom as well as orbital specific accuracy. The same protocol with a double hole particle relaxation also produced remarkably accurate K-edge spectra of core to valence hole excitation energies from the first (nO8π∗) and second (ππ∗) excited states of thymine, confirming the assignment of 1s → n excitation for the experimentally observed 526.4 eV peak. Regarding both accuracy and practicality, therefore, MRSF-TDDFT provides a promising protocol for core electron spectra both of ground and excited electronic states alike.


Item Type:Report or Paper (Discussion Paper)
Related URLs:
URLURL TypeDescription
https://doi.org/10.26434/chemrxiv-2022-mw4gpDOIDiscussion Paper
https://resolver.caltech.edu/CaltechAUTHORS:20221017-15547800.37Related ItemJournal article
ORCID:
AuthorORCID
Cho, Daeheum0000-0002-0322-4291
Lee, Seunghoon0000-0003-3665-587X
Huix-Rotllant, Miquel0000-0002-2131-7328
Choi, Cheol Ho0000-0002-8757-1396
Additional Information:The content is available under CC BY NC ND 4.0 License. This work was supported by the Samsung Science and Technology Foundations (SSTF-BA1701-12) for the fundamental theory developments and the NRF funded by the Ministry of Science and ICT (2020R1A2C2008246 and 2020R1A5A1019141). MAS and MHR acknowledge financial support by the “Agence Nationale pour la Recherche” through the project MULTICROSS (ANR-19-CE29-0018-01). Centre de Calcul Intensif d’Aix-Marseille is acknowledged for granting access to its high performance computing resources. We thank the financing through the program PHC STAR 2019 granted by the “ministère de l’Europe et des Affaires étrangères” (MEAE), the “ministère de l’Enseignement supérieur, de la Recherche et de l’Innovation” (MESRI) and the National Research Foundation of Korea (NRF). The author(s) have declared they have no conflict of interest with regard to this content.
Funders:
Funding AgencyGrant Number
Samsung Science and Technology FoundationSSTF-BA1701-12
National Research Foundation of Korea2020R1A2C2008246
National Research Foundation of Korea2020R1A5A1019141
Agence Nationale de la Recherche (ANR)ANR-19-CE29-0018-01
Ministère de l’Europe et des Affaires étrangères (MEAE)UNSPECIFIED
Ministère de l’Enseignement supérieur, de la Recherche et de l’Innovation (MESRI)UNSPECIFIED
Subject Keywords:x-ray absorption; mixed-reference spin-flip; time-dependent density-functional theory; core-hole pair
DOI:10.26434/chemrxiv-2022-mw4gp
Record Number:CaltechAUTHORS:20220705-346766000
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20220705-346766000
Official Citation:Park W, Alías-Rodríguez M, Cho D, Lee S, Huix-Rotllant M, Choi CH. Mixed-Reference Spin-Flip Time-Dependent Density Functional Theory for Accurate X-ray Absorption Spectroscopy. ChemRxiv. 2022. doi:10.26434/chemrxiv-2022-mw4gp
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:115345
Collection:CaltechAUTHORS
Deposited By: George Porter
Deposited On:07 Jul 2022 22:44
Last Modified:18 Oct 2022 21:37

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