Density functional theory study of the Jahn-Teller effect in cobaltocene

Abstract

A detailed discussion of the potential energy surface of bis(cyclopentadienyl)cobalt(II), cobaltocene, is given. Vibronic coupling coefficients are calculated using density functional theory (DFT). Results are in good agreement with experimental findings. On the basis of our calculation, there is no second-order Jahn-Teller (JT) effect as predicted by group theory. The JT distortion can be expressed as a linear combination of all totally symmetric normal modes of the low-symmetry, minimum-energy conformation. The out-ofplane ring deformation is the most important mode. The JT distortion is analyzed by seeking the path of minimal energy of the adiabatic potential energy surface.

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

“…In the JT semantics this is called the multimode problem. In this review the treatment of this problem using DFT recently proposed by us [86] is presented. The essence of our proposition is to express JT active distortion as a linear combination of all totally symmetric normal modes in the low symmetry minimum energy conformation.…”

Density Functional Theory for the Study of the Multimode Jahn-Teller Effect

“…Details can be found in our previous papers [5,13,14,15]. The considered molecules have a doubly degenerate electronic ground state, which is coupled with vibrations of a doubly degenerate irreducible representation in the HS point group, thus they belong to the E e JT systems.…”

“…and ring-tilt (9% to the R JT ; 55% to the E JT ); a 1 ' is metal-ring stretch (10% to the R JT ; 12% to the E JT ) [5,13,15].…”

DFT study of the Jahn–Teller effect in Cu(II) chelate complexes

“…Path from the HS to the LS minimum obtained in this way is the Intrinsic Distortion Path (IDP), which gives additional information about the microscopic origin and mechanism of the distortion. Details about this approach has been described in our previous papers [4,14].…”

“…Further motivation for this work comes from our continuous interest in systems where the JT distortion arises as a consequence of coupling of the electronic states with a number of different normal modes, so called multimode JT problem. Thus, in addition we performed the analysis of the multimode JT effect on the above mentioned systems using the method recently proposed by us [4,14].…”