General treatment of the multimode Jahn-Teller effect: study of fullerene cations

• Published in: Physical chemistry chemical physics : PCCP Vol. 15; no. 4; pp. 1252 - 1259
• Main Authors: Ramanantoanina, Harry, Zlatar, Matija, García-Fernández, Pablo, Daul, Claude, Gruden-Pavlovi, Maja
• Format: Journal Article
• Language: English
• Published: Cambridge Royal Society of Chemistry 28.01.2013
• Subjects: Apes; Cations; Chemistry; Constants; Coupling (molecular); Cross-disciplinary physics: materials science; rheology; Distortion; Exact sciences and technology; Fullerenes; Fullerenes and related materials; diamonds, graphite; General and physical chemistry; Jahn-Teller effect; Materials science; Mathematical models; Physics; Specific materials; Fullerenes; Jahn Teller effect
• ISSN: 1463-9076; 1463-9084; 1463-9084
• DOI: 10.1039/c2cp43591h

A general model for the analysis of the Adiabatic Potential Energy Surfaces (APES) of the molecules that are subject to the multimode Jahn-Teller effect is presented. The method utilizes the information obtained by DFT calculations on a distorted stationary point on the APES. The essence of the model is to express the distortion along a model minimal energy path called Intrinsic Distortion Path (IDP), projecting the geometry of the system on the normal modes of the either high-symmetry (HS) or low symmetry (LS) nuclear configuration. This allows us to determine the significance of all of the involved normal modes along a relevant particular path of distortion, and the direct calculation of the vibronic coupling constants. The IDP analysis is illustrated by the discussion of the multimode H ⊗ (g + 2h) JT effect in fullerene cations (C 60 + ) giving a deep insight into the origin and the mechanism of vibronic coupling in fullerene based molecules. A general approach, fully non-empirical, to analyse the multimode distortion using multideterminantal-DFT and Intrinsic Distortion Path methods has been presented and illustrated on C 60 + .