Exact two-component TDDFT with simple two-electron picture-change corrections: X-ray absorption spectra near L- and M-edges of four-component quality at two-component cost

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F70883521%3A28610%2F23%3A63560218" target="_blank" >RIV/70883521:28610/23:63560218 - isvavai.cz</a>

Result on the web

<a href="https://pubs.acs.org/doi/10.1021/acs.jpca.2c08307" target="_blank" >https://pubs.acs.org/doi/10.1021/acs.jpca.2c08307</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.jpca.2c08307" target="_blank" >10.1021/acs.jpca.2c08307</a>

Result language

angličtina

Original language name

Exact two-component TDDFT with simple two-electron picture-change corrections: X-ray absorption spectra near L- and M-edges of four-component quality at two-component cost

Original language description

X-ray absorption spectroscopy (XAS) has gained popularity in recent years as it probes matter with high spatial and elemental sensitivities. However, the theoretical modeling of XAS is a challenging task since XAS spectra feature a fine structure due to scalar (SC) and spin-orbit (SO) relativistic effects, in particular near L and M absorption edges. While full four-component (4c) calculations of XAS are nowadays feasible, there is still interest in developing approximate relativistic methods that enable XAS calculations at the two-component (2c) level while maintaining the accuracy of the parent 4c approach. In this article we present theoretical and numerical insights into two simple yet accurate 2c approaches based on an (extended) atomic mean-field exact two-component Hamiltonian framework, (e)amfX2C, for the calculation of XAS using linear eigenvalue and damped response time-dependent density functional theory (TDDFT). In contrast to the commonly used one-electron X2C (1eX2C) Hamiltonian, both amfX2C and eamfX2C account for the SC and SO two-electron and exchange-correlation picture-change (PC) effects that arise from the X2C transformation. As we demonstrate on L- and M-edge XAS spectra of transition metal and actinide compounds, the absence of PC corrections in the 1eX2C approximation results in a substantial overestimation of SO splittings, whereas (e)amfX2C Hamiltonians reproduce all essential spectral features such as shape, position, and SO splitting of the 4c references in excellent agreement, while offering significant computational savings. Therefore, the (e)amfX2C PC correction models presented here constitute reliable relativistic 2c quantum-chemical approaches for modeling XAS.

Czech name

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Czech description

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Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

—

OECD FORD branch

10301 - Atomic, molecular and chemical physics (physics of atoms and molecules including collision, interaction with radiation, magnetic resonances, Mössbauer effect)

Project

—

Continuities

V - Vyzkumna aktivita podporovana z jinych verejnych zdroju

Publication year

2023

Confidentiality

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Name of the periodical

Journal of Physical Chemistry A

ISSN

1089-5639

e-ISSN

—

Volume of the periodical

127

Issue of the periodical within the volume

5

Country of publishing house

US - UNITED STATES

Number of pages

17

Pages from-to

"1360–1376"

UT code for WoS article

000927032700001

EID of the result in the Scopus database

2-s2.0-85147524019