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

William P. Carbery, Archana Verma, Daniel Turner

Research output: Contribution to journalArticle

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 languageEnglish (US)
Pages (from-to)1315-1322
Number of pages8
JournalJournal of Physical Chemistry Letters
Volume8
Issue number6
DOIs
StatePublished - Mar 16 2017

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Transition metal compounds
metal compounds
intersections
Orbits
transition metals
orbits
Jahn-Teller effect
Angular momentum
Vibrational spectra
Excited states
electronic spectra
vibrational spectra
Laser pulses
angular momentum
Crystal structure
broadband
X rays
crystal structure
energy
pulses

ASJC Scopus subject areas

  • Materials Science(all)

Cite this

Spin-Orbit Coupling Drives Femtosecond Nonadiabatic Dynamics in a Transition Metal Compound. / Carbery, William P.; Verma, Archana; Turner, Daniel.

In: Journal of Physical Chemistry Letters, Vol. 8, No. 6, 16.03.2017, p. 1315-1322.

Research output: Contribution to journalArticle

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