Abstract

Intriguing vibronic patterns are found in the calculated spectra of hot allowed and cold forbidden Jahn-Teller (JT) progressions pertaining to A↔E⊗e electronic transitions. Formation of series containing JT progressions exhibiting similar allowed intensity patterns has been revealed. Excluding one important case, the first JT progressions of complementary such series in the “forward” and “reverse” electronic transitions show similar intensity patterns. Albeit breakdown of the Born-Oppenheimer approximation, certain JT progressions display intensity patterns which resemble those characteristic of normal Franck-Condon progressions. Hot JT progressions with several pronounced maxima occur. Vibronic patterns of hot allowed and cold forbidden intensity along correlated JT progressions are identical.

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