Spin-Orbit Coupling Drives Femtosecond Nonadiabatic Dynamics in a Transition Metal Compound

William P. Carbery, Archana Verma, Daniel B. Turner

Research output: Contribution to journalArticlepeer-review


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 languageEnglish (US)
Pages (from-to)1315-1322
Number of pages8
JournalJournal of Physical Chemistry Letters
Issue number6
StatePublished - Mar 16 2017

ASJC Scopus subject areas

  • General Materials Science
  • Physical and Theoretical Chemistry


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