Eur. Phys. J. D (2013) 67: 17
https://doi.org/10.1140/epjd/e2012-30522-5

Regular Article

Effect of structure and size on the excited states dynamics of CaAr_n clusters^*

¹ Departamento de Química Física, Facultad de Química, Universidad de Sevilla, 41012 Sevilla, Spain
² Laboratoire de Chimie et de Physique Quantique/IRSAMC, CNRS and Université de Toulouse (UPS), 118 route de Narbonne, 31062, Toulouse, France

^a e-mail: fernand.spiegelman@irsamc.ups-tlse.fr

Received: 23 August 2012
Received in final form: 29 October 2012
Published online: 5 February 2013

Abstract

The time-resolved photoelectron spectra, probing the non-adiabatic dynamics of CaAr_n clusters excited by a pump pulse in the vicinity of the 4s4p   ¹P line of calcium, are simulated. The simulations involve Diatomics-In-Molecules modelling of the excited electronic structure, excited states dynamics with electronic transitions, and classical approximations to derive the time-resolved photoelectron spectra. The oscillations in the time-dependence of the spectra, associated with the relative motion of calcium with respect to the argon cluster, and the corresponding nonadiabatic relaxation processes are analysed according to cluster size (n ≈ 55 and 147), structure (icosahedral versus cuboctahedral shape) and local environment (substitution versus surface deposition of calcium, surface type).