Jahn–Teller Effect and Spin-Orbit Coupling in Heavy Alkali Trimers

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

doi:10.1007/978-94-007-2384-9_16

Jahn–Teller Effect and Spin-Orbit Coupling in Heavy Alkali Trimers

Andreas W. Hauser^*
, Gerald Auböck
, Wolfgang E. Ernst

^*Corresponding author for this work

Institute of Experimental Physics (5110)

Research output: Chapter in Book/Report/Conference proceeding › Chapter › peer-review

Abstract

Triatomic alkali-metal clusters in their high-spin manifolds of electronically excited states provide the chance to investigate the spectroscopic consequences of the combination of Jahn–Teller effect and spin-orbit coupling with powerful methods of quantum chemistry such as open-shell coupled cluster approaches and multireference Rayleigh-Schroedinger perturbation theory. With respect to available experimental data the 2⁴E^′ ← 1⁴A₂ ^′ transitions are selected to document the quenching of the paradigmatic E ⊗ e Jahn–Teller distortion with increasing spin-orbit coupling. The simulated spectra for potassium, rubidium and cesium trimers are provided together with all relevant parameters such as harmonic frequencies, Jahn–Teller parameters and spin-orbit splittings obtained from the ab initio approach. Beside that, the molecular geometries and formation energies of these van der Waals molecules are also listed in this chapter.

Original language	English
Title of host publication	Progress in Theoretical Chemistry and Physics
Publisher	Springer Nature
Pages	301-316
Number of pages	16
ISBN (Print)	978-94-007-2383-2
DOIs	https://doi.org/10.1007/978-94-007-2384-9_16
Publication status	Published - 2012

Publication series

Name	Progress in Theoretical Chemistry and Physics
Volume	23
ISSN (Print)	1567-7354
ISSN (Electronic)	2215-0129

Keywords

Angular Momentum Projection
Electronic Angular Momentum
Magnetic Circular Dichroism
Magnetic Circular Dichroism Spectrum
Teller Effect

ASJC Scopus subject areas

General Chemistry
Biochemistry, Genetics and Molecular Biology (miscellaneous)
General Physics and Astronomy

Fields of Expertise

Advanced Materials Science

Treatment code (Nähere Zuordnung)

Basic - Fundamental (Grundlagenforschung)
Experimental

Cooperations

NAWI Graz

Access to Document

10.1007/978-94-007-2384-9_16

Cite this

@inbook{0e67dbf85a424f15b05f351f27fe0601,

title = "Jahn–Teller Effect and Spin-Orbit Coupling in Heavy Alkali Trimers",

abstract = "Triatomic alkali-metal clusters in their high-spin manifolds of electronically excited states provide the chance to investigate the spectroscopic consequences of the combination of Jahn–Teller effect and spin-orbit coupling with powerful methods of quantum chemistry such as open-shell coupled cluster approaches and multireference Rayleigh-Schroedinger perturbation theory. With respect to available experimental data the 24E ′ ← 14A2 ′ transitions are selected to document the quenching of the paradigmatic E ⊗ e Jahn–Teller distortion with increasing spin-orbit coupling. The simulated spectra for potassium, rubidium and cesium trimers are provided together with all relevant parameters such as harmonic frequencies, Jahn–Teller parameters and spin-orbit splittings obtained from the ab initio approach. Beside that, the molecular geometries and formation energies of these van der Waals molecules are also listed in this chapter.",

keywords = "Angular Momentum Projection, Electronic Angular Momentum, Magnetic Circular Dichroism, Magnetic Circular Dichroism Spectrum, Teller Effect",

author = "Hauser, \{Andreas W.\} and Gerald Aub{\"o}ck and Ernst, \{Wolfgang E.\}",

note = "Funding Information: Fig. 16.6 MCD spectra of the 24E′ ← 14A2′ transition in Cs3, plotted as a function of the SO splitting Δ. Positive MCD signal is scaled in red, negative signal in blue. Since the four main peaks are well separated over the observed range, no essential overlapping effects occur, and the structure is almost equal to the LIF structure of Fig. 16.5. The linear JT coupling parameter k is fixed to a value of 0.5525. The stick spectra are slightly broadened to improve the readability of the illustration (gaussian profile convolution, FHWM is set to 5 cm−1) Acknowledgments AWH gratefully acknowledges support from the Graz Advanced School of Science, a cooperation project between TU Graz and the University of Graz, and the Austrian Science Fund (FWF, Grant No. P19759-N20). Publisher Copyright: {\textcopyright} 2011, Springer Science+Business Media B.V.",

year = "2012",

doi = "10.1007/978-94-007-2384-9\_16",

language = "English",

isbn = "978-94-007-2383-2",

series = "Progress in Theoretical Chemistry and Physics",

publisher = "Springer Nature",

pages = "301--316",

booktitle = "Progress in Theoretical Chemistry and Physics",

address = "Germany",

}

TY - CHAP

T1 - Jahn–Teller Effect and Spin-Orbit Coupling in Heavy Alkali Trimers

AU - Hauser, Andreas W.

AU - Auböck, Gerald

AU - Ernst, Wolfgang E.

N1 - Funding Information: Fig. 16.6 MCD spectra of the 24E′ ← 14A2′ transition in Cs3, plotted as a function of the SO splitting Δ. Positive MCD signal is scaled in red, negative signal in blue. Since the four main peaks are well separated over the observed range, no essential overlapping effects occur, and the structure is almost equal to the LIF structure of Fig. 16.5. The linear JT coupling parameter k is fixed to a value of 0.5525. The stick spectra are slightly broadened to improve the readability of the illustration (gaussian profile convolution, FHWM is set to 5 cm−1) Acknowledgments AWH gratefully acknowledges support from the Graz Advanced School of Science, a cooperation project between TU Graz and the University of Graz, and the Austrian Science Fund (FWF, Grant No. P19759-N20). Publisher Copyright: © 2011, Springer Science+Business Media B.V.

PY - 2012

Y1 - 2012

N2 - Triatomic alkali-metal clusters in their high-spin manifolds of electronically excited states provide the chance to investigate the spectroscopic consequences of the combination of Jahn–Teller effect and spin-orbit coupling with powerful methods of quantum chemistry such as open-shell coupled cluster approaches and multireference Rayleigh-Schroedinger perturbation theory. With respect to available experimental data the 24E ′ ← 14A2 ′ transitions are selected to document the quenching of the paradigmatic E ⊗ e Jahn–Teller distortion with increasing spin-orbit coupling. The simulated spectra for potassium, rubidium and cesium trimers are provided together with all relevant parameters such as harmonic frequencies, Jahn–Teller parameters and spin-orbit splittings obtained from the ab initio approach. Beside that, the molecular geometries and formation energies of these van der Waals molecules are also listed in this chapter.

AB - Triatomic alkali-metal clusters in their high-spin manifolds of electronically excited states provide the chance to investigate the spectroscopic consequences of the combination of Jahn–Teller effect and spin-orbit coupling with powerful methods of quantum chemistry such as open-shell coupled cluster approaches and multireference Rayleigh-Schroedinger perturbation theory. With respect to available experimental data the 24E ′ ← 14A2 ′ transitions are selected to document the quenching of the paradigmatic E ⊗ e Jahn–Teller distortion with increasing spin-orbit coupling. The simulated spectra for potassium, rubidium and cesium trimers are provided together with all relevant parameters such as harmonic frequencies, Jahn–Teller parameters and spin-orbit splittings obtained from the ab initio approach. Beside that, the molecular geometries and formation energies of these van der Waals molecules are also listed in this chapter.

KW - Angular Momentum Projection

KW - Electronic Angular Momentum

KW - Magnetic Circular Dichroism

KW - Magnetic Circular Dichroism Spectrum

KW - Teller Effect

UR - https://www.scopus.com/pages/publications/84901945022

U2 - 10.1007/978-94-007-2384-9_16

DO - 10.1007/978-94-007-2384-9_16

M3 - Chapter

SN - 978-94-007-2383-2

T3 - Progress in Theoretical Chemistry and Physics

SP - 301

EP - 316

BT - Progress in Theoretical Chemistry and Physics

PB - Springer Nature

ER -

Jahn–Teller Effect and Spin-Orbit Coupling in Heavy Alkali Trimers

Abstract

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Keywords

ASJC Scopus subject areas

Fields of Expertise

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Helium Nanodroplets

EU - Cold Molecules HPRN-CT-20 - Cold Molecules: Formation, Trapping and Dynamics

Cite this

Jahn–Teller Effect and Spin-Orbit Coupling in Heavy Alkali Trimers

Abstract

Publication series

Keywords

ASJC Scopus subject areas

Fields of Expertise

Treatment code (Nähere Zuordnung)

Cooperations

Access to Document

Other files and links

Fingerprint

Projects

Helium Nanodroplets

EU - Cold Molecules HPRN-CT-20 - Cold Molecules: Formation, Trapping and Dynamics

Cite this