A New Method to Describe the Multimode Jahn–Teller Effect Using Density Functional Theory
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 intersectionsSource:
The Jahn-Teller Effect Fundamentals and Implications for Physics and Chemistry - Springer Series in Chemical Physics, 2009, 97, 131-165Publisher:
- Springer, Berlin, Heidelberg
Funding / 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
Collections
Institution/Community
IHTMTY - CHAP AU - Zlatar, Matija AU - Schläpfer, Carl-Wilhelm AU - Daul, Claude PY - 2009 UR - https://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 -
@inbook{ author = "Zlatar, Matija and Schläpfer, Carl-Wilhelm and Daul, Claude", year = "2009", 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", booktitle = "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.. (2009). A New Method to Describe the Multimode Jahn–Teller Effect Using Density Functional Theory. in The Jahn-Teller Effect Fundamentals and Implications for Physics and Chemistry - Springer Series in Chemical Physics Springer, Berlin, Heidelberg., 97, 131-165. https://doi.org/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. in The Jahn-Teller Effect Fundamentals and Implications for Physics and Chemistry - Springer Series in Chemical Physics. 2009;97:131-165. doi: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" in The Jahn-Teller Effect Fundamentals and Implications for Physics and Chemistry - Springer Series in Chemical Physics, 97 (2009):131-165, https://doi.org/10.1007/978-3-642-03432-9_6 . .