Photodissociation of I ₂ ⁻ (Ar) _n Clusters Studied with Anion Femtosecond Photoelectron Spectroscopy

Abstract

Anion femtosecond photoelectron spectroscopy was used to follow the dynamics of the I 2 − (Ar) 6 and I 2 − (Ar) 20 clusters subsequent to photodissociation of the I 2 − chromophore. The experiments showed that photodissociation of the I 2 − moiety in I 2 − (Ar) 6 is complete by approximately 200 femtoseconds, just as in bare I 2 − , but also that attractive interactions between the departing anion fragment and the solvent atoms persisted for 1200 femtoseconds. Photodissociation of I 2 − (Ar) 20 results in caging of the I 2 − followed by recombination and vibrational relaxation on the excited à 2 Π g ,3/2 and the ground X̃ 2 Σ u + states; these processes are complete in 35 and 200 picoseconds, respectively.

Global Minimum‐Energy Structure and Spectroscopic Properties of I2.−⋅n H2O Clusters: A Monte Carlo Simulated Annealing Study

“…Anion femtosecond photoelectron spectroscopy has been used to follow the dynamics of I 2 C À ·n Ar clusters subsequent to photodissociation of the I 2 C À chromophore. [42] Photodissociation, geminate recombination, and relaxation dynamics were investigated in size-selected I 2 C À ·n Ar clusters by using a coupled quantum-classical MD procedure and a model Hamiltonian. [43] However, till now only one theoretical study on hydrated I 2 C À cluster has been reported in the literature.…”

Femtosecond Time-Resolved Photoelectron Spectroscopy

“…The pioneering work by Lineberger and co-workers [187][188][189][190][191] papers. [198][199][200][201] The maximum sizes in both cases represent complete solvent shells. In all the clusters, dissociation of the I 2 -chromophore subsequent to excitation of the A′ 2 Π g,1/2 r X 2 Σ u + occurs on a time scale similar to that of bare I 2 -, 200-300 fs, resulting in the production of solvated I -within the cluster.…”

Substituent Effects in Molecular Electronic Relaxation Dynamics via Time-Resolved Photoelectron Spectroscopy: ππ* States in Benzenes

“…Its application to polyatomic nonadiabatic dynamics was proposed theoretically over 10 years ago 4 and first demonstrated for the case of S 1 -S 0 internal conversion in hexatriene. 5 TRPES has been applied to wave packet dynamics in simple systems, 6-10 intramolecular vibrational energy redistribution, 11 internal conversion, 12-18 photodissociation dynamics, 19,20 intersystem crossing, 21,22 intracluster reaction dynamics, 23 and excited-state intramolecular protontransfer dynamics. 24 The outgoing photoelectron may also be differentially analyzed as a function of time with respect to angular distribution.…”