A combined experimental and computational investigation of the microscopic external heavy atom effect in van der Waals clusters.
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.
Doyle
Richard J
RJ
Department of Chemistry, University of Warwick, Coventry CV4 7AL, United Kingdom.
Da Campo
Raffaello
R
Taylor
Peter R
PR
Mackenzie
Stuart R
SR