Four-Component Polarization Propagator Calculations of Electron Excitations: Spectroscopic Implications of Spin-Orbit Coupling Effects

Markus Pernpointner, Lucas Visscher, Alexander B. Trofimov

Research output: Contribution to JournalArticleAcademicpeer-review

Abstract

A complete implementation of the polarization propagator based on the Dirac-Coulomb Hamiltonian is presented and applied to excitation spectra of various systems. Hereby the effect of spin-orbit coupling on excitation energies and transition moments is investigated in detail. The individual perturbational contributions to the transition moments could now be separately analyzed for the first time and show the relevance of one- and two-particle terms. In some systems different contributions to the transition moments partially cancel each other and do not allow for simple predictions. For the outer valence spectrum of the H2Os(CO)4 complex a detailed final state analysis is performed explaining the sensitivity of the excitation spectrum to spin-orbit effects. Finally, technical issues of handling double group symmetry in the relativistic framework and methodological aspects of our parallel implementation are discussed.

Original languageEnglish
Pages (from-to)1510-1522
Number of pages13
JournalJournal of Chemical Theory and Computation
Volume14
Issue number3
Early online date22 Jan 2018
DOIs
Publication statusPublished - 13 Mar 2018

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Orbits
Polarization
orbits
moments
Hamiltonians
propagation
Electrons
Excitation energy
polarization
Carbon Monoxide
Electron transitions
excitation
electrons
valence
sensitivity
symmetry
predictions
energy

Cite this

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title = "Four-Component Polarization Propagator Calculations of Electron Excitations: Spectroscopic Implications of Spin-Orbit Coupling Effects",
abstract = "A complete implementation of the polarization propagator based on the Dirac-Coulomb Hamiltonian is presented and applied to excitation spectra of various systems. Hereby the effect of spin-orbit coupling on excitation energies and transition moments is investigated in detail. The individual perturbational contributions to the transition moments could now be separately analyzed for the first time and show the relevance of one- and two-particle terms. In some systems different contributions to the transition moments partially cancel each other and do not allow for simple predictions. For the outer valence spectrum of the H2Os(CO)4 complex a detailed final state analysis is performed explaining the sensitivity of the excitation spectrum to spin-orbit effects. Finally, technical issues of handling double group symmetry in the relativistic framework and methodological aspects of our parallel implementation are discussed.",
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Four-Component Polarization Propagator Calculations of Electron Excitations: Spectroscopic Implications of Spin-Orbit Coupling Effects. / Pernpointner, Markus; Visscher, Lucas; Trofimov, Alexander B.

In: Journal of Chemical Theory and Computation, Vol. 14, No. 3, 13.03.2018, p. 1510-1522.

Research output: Contribution to JournalArticleAcademicpeer-review

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T1 - Four-Component Polarization Propagator Calculations of Electron Excitations: Spectroscopic Implications of Spin-Orbit Coupling Effects

AU - Pernpointner, Markus

AU - Visscher, Lucas

AU - Trofimov, Alexander B.

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AB - A complete implementation of the polarization propagator based on the Dirac-Coulomb Hamiltonian is presented and applied to excitation spectra of various systems. Hereby the effect of spin-orbit coupling on excitation energies and transition moments is investigated in detail. The individual perturbational contributions to the transition moments could now be separately analyzed for the first time and show the relevance of one- and two-particle terms. In some systems different contributions to the transition moments partially cancel each other and do not allow for simple predictions. For the outer valence spectrum of the H2Os(CO)4 complex a detailed final state analysis is performed explaining the sensitivity of the excitation spectrum to spin-orbit effects. Finally, technical issues of handling double group symmetry in the relativistic framework and methodological aspects of our parallel implementation are discussed.

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