Exact zero-point energy shift in thee⊗(nE),t⊗(nH)many-modes dynamic Jahn-Teller systems at strong coupling

Abstract

We find the exact semiclassical (strong coupling) zero-point energy shifts applicable to the $e\otimes \mathrm{}\left(\mathrm{nE}\right)\mathrm{}$ and $t\otimes \mathrm{}\left(\mathrm{nH}\right)\mathrm{}$ dynamic Jahn-Teller problems, for an arbitrary number $n$ of discrete vibrational modes simultaneously coupled to one single electronic level. We also obtain an analytical formula for the frequency of the resulting normal modes, which has an attractive and apparently general Slater-Koster form. The limits of validity of this approach are assessed by comparison with O’Brien’s previous effective-mode approach, and with accurate numerical diagonalizations. Numerical values obtained for $t\otimes \mathrm{}\left(\mathrm{nH}\right)\mathrm{}$ with $n=8\mathrm{}$ and coupling constants appropriate to ${\mathrm{C}}_{60}^{-}$ are used for this purpose, and are discussed in the context of fullerene.