title: A combined experimental and computational investigation of the microscopic external heavy atom effect in van der Waals clusters.
abstract: We present a combined experimental and computational study of the external heavy atom effect in van der Waals clusters of para-difluorobenzene (pDFB) with rare-gas atoms. Experimentally, clustering with rare-gas atoms is observed to shorten significantly the S1 fluorescence lifetime compared with that of the pDFB monomer, an effect we interpret in terms of an enhancement of the S1-T1 intersystem crossing rate. In order to test the validity of this widely held assumption, we have calculated the S1-T1 spin-orbit coupling matrix elements in the X-pDFB complexes (X=Ne, Ar, Kr) using a multiconfigurational linear response approach.
authors.affiliation: Department of Chemistry, University of Warwick, Coventry CV4 7AL, United Kingdom.
authors.forename: Richard J
authors.initials: RJ
authors.lastname: Doyle
authors.forename: Raffaello
authors.initials: R
authors.lastname: Da Campo
authors.forename: Peter R
authors.initials: PR
authors.lastname: Taylor
authors.forename: Stuart R
authors.initials: SR
authors.lastname: Mackenzie