title: Hg-Xe exciplex formation in mixed Xe/Ar matrices: molecular dynamics and luminescence study.
abstract: Luminescence of Hg((3)P1) atoms trapped in mixed Ar/Xe matrices containing a small amount of Xe is reported. Broad emission bands, strongly red-shifted from absorption are recorded which are assigned to strong complexes formed between the excited mercury Hg* and xenon atoms. Molecular dynamics calculations are performed on simulated Xe/Ar samples doped with Hg to follow the behavior of Hg* in the mixed rare gas matrices leading to exciplex formation. The role of Xe atoms in the first solvation shell (SS1) around Hg was investigated in detail, revealing the formation of two kinds of triatomic exciplexes; namely, Xe-Hg*-Xe and Ar-Hg*-Xe. The first species exists only when two xenon atoms are present in SS1 with specific geometries allowing the formation of a linear or quasi-linear exciplex. In the other geometries, or in the presence of only one Xe in SS1, a linear Ar-Hg*-Xe exciplex is formed. The two kinds of exciplexes have different emission bands, the most red-shifted being that involving two Xe atoms, whose emission is very close to that observed in pure Xe matrices. Simulations give a direct access to the analysis of the experimental absorption, emission, and excitation spectra, together with the dynamics of exciplexes formation.
authors.affiliation: †Departamento de Física General, Matemática y Computación, Instituto Superior de Tecnologías y Ciencias Aplicadas, La Habana, Cuba.
authors.forename: Rolando
authors.initials: R
authors.lastname: Lozada-García
authors.affiliation: †Departamento de Física General, Matemática y Computación, Instituto Superior de Tecnologías y Ciencias Aplicadas, La Habana, Cuba.
authors.forename: Germán
authors.initials: G
authors.lastname: Rojas-Lorenzo
authors.affiliation: ‡Institut des Sciences Moléculaires d'Orsay (ISMO)- UMR 8214, CNRS-Université Paris-Sud, Bâtiment 210 Université Paris-Sud, F-91405 Orsay, France.
authors.forename: Claudine
authors.initials: C
authors.lastname: Crépin
authors.affiliation: §Department of Chemistry, National University of Ireland-Maynooth, Maynooth, Co., Kildare, Ireland.
authors.forename: Maryanne
authors.initials: M
authors.lastname: Ryan
authors.affiliation: §Department of Chemistry, National University of Ireland-Maynooth, Maynooth, Co., Kildare, Ireland.
authors.forename: John G
authors.initials: JG
authors.lastname: McCaffrey