TY - JOUR A1 - Hartmann, Michael A1 - Pittner, Jiřı́ A1 - Dam, Huub van A1 - Bonačić-Koutecký, Vlasta T1 - Theoretical study of femtosecond pump–probe signals of nonstoichiometric alkali halide clusters JF - The European Physical Journal D N2 - We present the outline of the ab–initio molecular dynamics method for adiabatic excited states which is suitable to treat the involved excited electronic states simultaneously with the motion of the nuclei. The method allows the simulation of time–resolved pump–probe signals and the analysis of the signals in terms of the underlying nuclear dynamics. Moreover, the timescales of the structural relaxation in excited electronic states vs. intramolecular vibrational relaxation processes can be estimated and the influence of the initial temperature of the cluster can be determined. The method is applied to the analysis of the timescales as well as of the dynamics of localized/delocalized electronic excitations in the Na2F molecule which represents a test example for nonstoichiometric alkali–halides with one excess electron. The aim is to develop a method for the investigation of time–dependent laser induced processes in clusters which is capable to extract the leading physical effects responsible for the controlled excitation dynamics and for the evolution of the non–equilibrium states. KW - Physics KW - Optical physics KW - Molecular physics Y1 - 1999 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:0298-opus4-5640 VL - 9 IS - 1 SP - 393 EP - 397 ER - TY - JOUR A1 - Hartmann, Michael A1 - Pittner, Jiřı́ A1 - Dam, Huub van A1 - Veyret, Vincent A1 - Bonacic-Koutecký, Vlasta T1 - Theoretical exploration of stationary and of ultrafast spectroscopy of small clusters JF - Applied Physics B N2 - Stationary spectra offer information on the interplay between the structures and the nature of electronic excitations reflecting bonding properties, as shown by comparing Sin with Agn (n=4-6) clusters. In order to study the dynamical properties, simulations and analysis of femtosecond (fs) time-resolved pump–probe or pump–dump signals have been carried out, which allows us to determine the timescales and the nature of configurational changes versus internal vibrational relaxation (IVR) in electronic ground or excited states. For this purpose we have developed a multi-state ab initio molecular dynamics (involving ground as well as adiabatic or non-adiabatic excited electronic states) on the timescale of the nuclear motion, using the time evolution of a thermal ensemble in the Wigner representation. The combination of ab initio quantum-chemical methods used for the molecular dynamics ‘on the fly’ and the Wigner-distribution approach for the description of the motion of the nuclei also allowed the accurate determination of pump–probe and pump–dump signals under temperature-dependent initial conditions. We use this novel combination of methods to investigate the dynamics in excited states of non-stoichiometric NanFn-1 clusters with a single excess electron. The timescales of the structural relaxation in excited states versus intramolecular vibrational relaxation processes have been determined, as illustrated for the example of Na4F3. This is the first study of the system with 15 degrees of freedom for which the dynamics in the excited states has been carried out without the precalculation of the energy surfaces. KW - Physics KW - Laser technology KW - Engineering Y1 - 2000 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:0298-opus4-5693 VL - 71 IS - 3 SP - 343 EP - 349 ER -