Spectral signatures of inter-system crossing mediated by energetically distant doorway levels: examples from the acetylene S1 state

Kyle L Bittinger; Wilton L Virgo; Robert W Field

doi:10.1021/jp2037894

Spectral signatures of inter-system crossing mediated by energetically distant doorway levels: examples from the acetylene S1 state

J Phys Chem A. 2011 Nov 3;115(43):11921-43. doi: 10.1021/jp2037894. Epub 2011 Sep 29.

Authors

Kyle L Bittinger¹, Wilton L Virgo, Robert W Field

Affiliation

¹ Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA.

PMID: 21913705
DOI: 10.1021/jp2037894

Abstract

We review recent research on the acetylene S(1) state that illustrates how mechanistic rather than phenomenological information about intersystem crossing (ISC) may be obtained directly from frequency-domain spectra. The focus is on the dynamically rich "doorway-mediated" ISC domain that lies between isolated spectroscopic spin-orbit perturbations and statistical-limit interactions between one singlet "bright state" and a quasi-continuum of triplet "dark states". New and improved experimental and data processing techniques permit the statistical-model curtain to be drawn back to reveal mechanistically explicit pathways via one or more identifiable, hence, manipulatable, doorway states, between a user-selected bright state and the undifferentiated bath of dark states.