Vibronic States of Octahedral Complexes

Abstract

The interactions which occur between nuclear and electronic motions in electronically degenerate states of octahedral molecules are investigated.frequency" polarizations of the electronic motions: if V is the electronic Hamiltonian, which difFers from the total Hamiltonian in the absence of the nuclear kinetic energies alone, then

Two-photon excitation spectroscopy of Cr3+:K2NaScF6elpasolite: II. Theoretical models

“…The dynamic Jahn-Teller effect prevails in the weak coupling regime, where H e and T N are comparable [16][17][18]. The matrices U j ( , , τ ) generally do not commute and cannot be diagonalized simultaneously; consequently, the electronic and vibrational motions are inextricably linked in vibronic wave functions, (14) with energy eigenvalues…”

Jahn–Teller Trajectories

“…If ax = a,, = wr, the trajectory represented by (2) becomes an ellipse the plane of whose orbit possesses a normal with direction cosines proportional to Multiplication of the right-hand sides of Eqs. (2) by these quantities and addition yields zero, showing that the trajectory lies in a plane passing through the origin E. It is more difficult to confirm the elliptical nature of the trajectory from (2); in fact, it is simplest to return to the equation of motion r = -w2r and appeal to the well-known result for an isotropic threedimensional harmonic o~cillator.~ For isotropic media we have wx = a,, = a,.…”

The Jahn–Teller effect in the lowest charge transfer state of UF6

“…In linear JT theory the distortion can be easily related to the JT stabilization energy , E JT. It is expected that this approximation will improve as E JT increases; dynamic effects Involving the various potential sur faces decrease (8) as the di stor ti on becomes predomi nant.…”

“…The distorted geometry and general surface topology of a T ig x t 2g m olecule are wel l known (8). The conditions for minima in the potential energy surfaces are I q~~I = I q~~I !…”