A New Method to Describe the Multimode Jahn–Teller Effect Using Density Functional Theory

Zlatar, Matija; Schläpfer, Carl-Wilhelm; Daul, Claude

doi:10.1007/978-3-642-03432-9_6

2009

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Authors

Zlatar, Matija

Schläpfer, Carl-Wilhelm
Daul, Claude

Book part (Accepted Version)

Springer-Verlag Berlin Heidelberg 2009

Metadata

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Abstract

A new method for the analysis of the adiabatic potential energy surfaces of Jahn–Teller (JT) active molecules is presented. It is based on the analogy between the JT distortion and reaction coordinates. Within the harmonic approximation the JT distortion can be analysed as the linear combination of all totally symmetric normal modes in the low symmetry minimum energy conformation. Contribution of the normal modes to the distortion, their energy contribution to the JT stabilisation energy, the forces at high symmetry cusp and detailed distortion path can be estimated quantitatively. This approach gives direct insight into the coupling of electronic structure and nuclear displacements. Further more, it is reviewed how multideterminental DFT can be applied for the calculation of the JT parameters. As examples the results for VCl4, cyclopentadienyl radical and cobaltocene are given.

Keywords:

Jahn-Teller effect / Potential Energy Surface / Vibronic Coupling / Normal Modes / Density Functional Theory / DFT calculations / Degenerate electronic states / Reaction coordinate / Conical intersections

Source:
The Jahn-Teller Effect Fundamentals and Implications for Physics and Chemistry - Springer Series in Chemical Physics, 2009, 97, 131-165

Publisher:

Springer, Berlin, Heidelberg

Projects:

Hemijske i biohemijske konsekvence metal-ligand interakcija, II. deo (RS-142017)
Swiss National Science Foundation

Note:

This is the author's version of the accepted, peer-reviewed chapter: Zlatar M., Schläpfer CW., Daul C. (2009) A New Method to Describe the Multimode Jahn–Teller Effect Using Density Functional Theory. In: Köppel H., Yarkony D., Barentzen H. (eds) The Jahn-Teller Effect. Springer Series in Chemical Physics, vol 97. Springer, Berlin, Heidelberg. DOI: https://doi.org/10.1007/978-3-642-03432-9_6
Published version: http://cer.ihtm.bg.ac.rs/handle/123456789/3092

DOI: 10.1007/978-3-642-03432-9_6

ISBN: 978-3-642-03431-2

ISSN: 0172-6218

WoS: 000292113400006

Scopus: 2-s2.0-78149488770

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	9
	24

TY  - CHAP
AU  - Zlatar, Matija
AU  - Schläpfer, Carl-Wilhelm
AU  - Daul, Claude
PY  - 2009
UR  - http://cer.ihtm.bg.ac.rs/handle/123456789/2665
AB  - A new method for the analysis of the adiabatic potential energy surfaces
of Jahn–Teller (JT) active molecules is presented. It is based on the analogy between
the JT distortion and reaction coordinates. Within the harmonic approximation the
JT distortion can be analysed as the linear combination of all totally symmetric
normal modes in the low symmetry minimum energy conformation. Contribution
of the normal modes to the distortion, their energy contribution to the JT stabilisation
energy, the forces at high symmetry cusp and detailed distortion path can
be estimated quantitatively. This approach gives direct insight into the coupling of
electronic structure and nuclear displacements. Further more, it is reviewed how
multideterminental DFT can be applied for the calculation of the JT parameters. As
examples the results for VCl4, cyclopentadienyl radical and cobaltocene are given.
PB  - Springer, Berlin, Heidelberg
T2  - The Jahn-Teller Effect Fundamentals and Implications for Physics and Chemistry - Springer Series in Chemical Physics
T1  - A New Method to Describe the Multimode Jahn–Teller Effect Using Density Functional Theory
VL  - 97
SP  - 131
EP  - 165
DO  - 10.1007/978-3-642-03432-9_6
ER  -

@article{
author = "Zlatar, Matija and Schläpfer, Carl-Wilhelm and Daul, Claude",
year = "2009",
url = "http://cer.ihtm.bg.ac.rs/handle/123456789/2665",
abstract = "A new method for the analysis of the adiabatic potential energy surfaces
of Jahn–Teller (JT) active molecules is presented. It is based on the analogy between
the JT distortion and reaction coordinates. Within the harmonic approximation the
JT distortion can be analysed as the linear combination of all totally symmetric
normal modes in the low symmetry minimum energy conformation. Contribution
of the normal modes to the distortion, their energy contribution to the JT stabilisation
energy, the forces at high symmetry cusp and detailed distortion path can
be estimated quantitatively. This approach gives direct insight into the coupling of
electronic structure and nuclear displacements. Further more, it is reviewed how
multideterminental DFT can be applied for the calculation of the JT parameters. As
examples the results for VCl4, cyclopentadienyl radical and cobaltocene are given.",
publisher = "Springer, Berlin, Heidelberg",
journal = "The Jahn-Teller Effect Fundamentals and Implications for Physics and Chemistry - Springer Series in Chemical Physics",
title = "A New Method to Describe the Multimode Jahn–Teller Effect Using Density Functional Theory",
volume = "97",
pages = "131-165",
doi = "10.1007/978-3-642-03432-9_6"
}

Zlatar M, Schläpfer C, Daul C. A New Method to Describe the Multimode Jahn–Teller Effect Using Density Functional Theory. The Jahn-Teller Effect Fundamentals and Implications for Physics and Chemistry - Springer Series in Chemical Physics. 2009;97:131-165

Zlatar, M., Schläpfer, C.,& Daul, C. (2009). A New Method to Describe the Multimode Jahn–Teller Effect Using Density Functional Theory.
The Jahn-Teller Effect Fundamentals and Implications for Physics and Chemistry - Springer Series in Chemical PhysicsSpringer, Berlin, Heidelberg., 97, 131-165.
https://doi.org/10.1007/978-3-642-03432-9_6

Zlatar Matija, Schläpfer Carl-Wilhelm, Daul Claude, "A New Method to Describe the Multimode Jahn–Teller Effect Using Density Functional Theory" 97 (2009):131-165,
https://doi.org/10.1007/978-3-642-03432-9_6 .