Abstract
Transient absorption measurements conducted using broadband, 6 fs laser pulses reveal unexpected femtosecond dynamics in the [IrBr6]2- model system. Vibrational spectra and the X-ray crystal structure indicate that these dynamics are not induced by a Jahn-Teller distortion, a type of conical intersection typically associated with the spectral features of transition metal compounds. Two-dimensional electronic spectra of [IrBr6]2- contain 23 cross peaks, which necessarily arise from spin-orbit coupling. Real-valued 2D spectra support a spectroscopic basis where strong nonadiabatic coupling, ascribed to multiple conical intersections, mediates rapid energy relaxation to the lowest-energy excited state. Subsequent analysis gives rise to a more generalized description of a conical intersection as a degeneracy between two adiabatic states having the same total angular momentum.
Original language | English (US) |
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Pages (from-to) | 1315-1322 |
Number of pages | 8 |
Journal | Journal of Physical Chemistry Letters |
Volume | 8 |
Issue number | 6 |
DOIs | |
State | Published - Mar 16 2017 |
ASJC Scopus subject areas
- General Materials Science
- Physical and Theoretical Chemistry