Relativistic Jahn-Teller effects in the quartet states of K3 and Rb3: A vibronic analysis of the 2 4E ′ 1 4A 2′ electronic transitions based on ab initio calculations

Andreas W. Hauser; Gerald Auböck; Carlo Callegari; Wolfgang E. Ernst

doi:10.1063/1.3394015

Relativistic Jahn-Teller effects in the quartet states of K₃ and Rb₃: A vibronic analysis of the 2 ⁴E ′ 1 ⁴A 2′ electronic transitions based on ab initio calculations

Andreas W. Hauser, Gerald Auböck, Carlo Callegari, Wolfgang E. Ernst

Graz University of Technology (90000)

Research output: Contribution to journal › Article › peer-review

Abstract

We apply second-order multireference Rayleigh-Schrödinger perturbation theory to obtain the adiabatic potential energy surface of the 1 ⁴A 2′ lowest quartet state and the 2 ⁴E ′ excited state of K₃ and Rb₃. Both trimers show a typical Ee Jahn-Teller distortion in their 2⁴E ′ state, which is analyzed in terms of relativistic Jahn-Teller effect theory. Linear, quadratic, and spin-orbit coupling terms are extracted from the ab initio results and used to generate simulated spectra for a direct comparison with laser-induced fluorescence and magnetic circular dichroism spectra of alkali-doped helium nanodroplets [Auböck, J. Chem. Phys. 129, 114501 (2008)].

Original language	English
Article number	164310
Journal	The Journal of Chemical Physics
Volume	132
Issue number	16
DOIs	https://doi.org/10.1063/1.3394015
Publication status	Published - 28 Apr 2010

ASJC Scopus subject areas

Physics and Astronomy(all)
Physical and Theoretical Chemistry

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Relativistic Jahn-Teller effects in the quartet states of K₃ and Rb₃: A vibronic analysis of the 2 ⁴E ′ 1 ⁴A 2′ electronic transitions based on ab initio calculations. / Hauser, Andreas W.; Auböck, Gerald; Callegari, Carlo et al.
In: The Journal of Chemical Physics, Vol. 132, No. 16, 164310, 28.04.2010.

Research output: Contribution to journal › Article › peer-review

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abstract = "We apply second-order multireference Rayleigh-Schr{\"o}dinger perturbation theory to obtain the adiabatic potential energy surface of the 1 4A 2′ lowest quartet state and the 2 4E ′ excited state of K3 and Rb3. Both trimers show a typical Ee Jahn-Teller distortion in their 24E ′ state, which is analyzed in terms of relativistic Jahn-Teller effect theory. Linear, quadratic, and spin-orbit coupling terms are extracted from the ab initio results and used to generate simulated spectra for a direct comparison with laser-induced fluorescence and magnetic circular dichroism spectra of alkali-doped helium nanodroplets [Aub{\"o}ck, J. Chem. Phys. 129, 114501 (2008)].",

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AU - Ernst, Wolfgang E.

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N2 - We apply second-order multireference Rayleigh-Schrödinger perturbation theory to obtain the adiabatic potential energy surface of the 1 4A 2′ lowest quartet state and the 2 4E ′ excited state of K3 and Rb3. Both trimers show a typical Ee Jahn-Teller distortion in their 24E ′ state, which is analyzed in terms of relativistic Jahn-Teller effect theory. Linear, quadratic, and spin-orbit coupling terms are extracted from the ab initio results and used to generate simulated spectra for a direct comparison with laser-induced fluorescence and magnetic circular dichroism spectra of alkali-doped helium nanodroplets [Auböck, J. Chem. Phys. 129, 114501 (2008)].

AB - We apply second-order multireference Rayleigh-Schrödinger perturbation theory to obtain the adiabatic potential energy surface of the 1 4A 2′ lowest quartet state and the 2 4E ′ excited state of K3 and Rb3. Both trimers show a typical Ee Jahn-Teller distortion in their 24E ′ state, which is analyzed in terms of relativistic Jahn-Teller effect theory. Linear, quadratic, and spin-orbit coupling terms are extracted from the ab initio results and used to generate simulated spectra for a direct comparison with laser-induced fluorescence and magnetic circular dichroism spectra of alkali-doped helium nanodroplets [Auböck, J. Chem. Phys. 129, 114501 (2008)].

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Relativistic Jahn-Teller effects in the quartet states of K₃ and Rb₃: A vibronic analysis of the 2 ⁴E ′ 1 ⁴A 2′ electronic transitions based on ab initio calculations

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