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Updated: Aug 23, 2026

Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry
Published on: April 8, 2020
A combined experimental and computational investigation of the microscopic external heavy atom effect in van der
Richard J Doyle1, Raffaello Da Campo, Peter R Taylor
1Department of Chemistry, University of Warwick, Coventry CV4 7AL, United Kingdom.
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.
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