The Franck-Condon (FC) approximation is used to obtain
analytical values for the second-order factors describing
vibronic reduction for the case of the strongly coupled
icosahedral T1u⊗hg Jahn-Teller (JT) system in
which an electronic triplet ground state is coupled to
vibrations of fivefold degeneracy. This is believed to be
applicable to the ground state of the C60- ion and so
the calculations should help in providing valuable physical
information on this fullerene ion. The procedures for
determining vibronic reduction effects depend critically on the
particular JT system and upon the vibronic coupling strength. In
the FC approximation, the major contributions to these reduction
factors originate from virtual vertical transitions between the
ground electronic adiabatic state and excited vibronic states
associated with upper sheets in the adiabatic potential energy
surface. At strong coupling, other transitions may be neglected.
The FC results are compared with those obtained from an
alternative approach involving a shift transformation. Details
are given for perturbations containing orbital operators of
threefold (T1) and fivefold (H) symmetry. The
discussion emphasizes the inherent high symmetry of the system.
First- and second-order vibronic reduction factors are
calculated analytically for the H⊗(g⊕h) Jahn-Teller system in Ih symmetry. Results are given
as a function of the strength of the coupling of the H orbital
to the vibrations of h and g symmetries. As the product
systems H⊗g and H⊗h contain repeated
representations, the calculations of many of the reduction
factors are more complicated than in other systems. These
complications and their implications are analysed in detail.
This system models the ground state of hole-doped C60
material, which has possible applications for high-temperature
superconductivity.
Analytical expressions for the vibronic states and energy spectrum of the icosahedral G ⊗ (g ⊕ h) Jahn-Teller system are derived. From these states, expressions for first-and second-order vibronic reduction factors are determined as a function of the strengths of the coupling of the G orbital to the g and h modes of vibration. The possibility of the vibronic ground state being a singlet A state, rather than the G state that would be expected in the absence of vibronic coupling, is explored. The reduction factors obtained provide a convenient basis for the modelling of spectra involving some of the excited states of the fullerene molecule C 60 and related ions.
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