Wave packet molecular dynamics

Schinke R and Huber J R 1995 Molecular dynamics in excited electronic states—time-dependent wave packet studies Femtosecond Chemistry Proc. Berlin Conf. Femtosecond Chemistry (Berlin, March 1993) (Weinheim Verlag Chemie)... 

Molecular spectroscopy offers a fiindamental approach to intramolecular processes [18, 94]. The spectral analysis in temis of detailed quantum mechanical models in principle provides the complete infomiation about the wave-packet dynamics on a level of detail not easily accessible by time-resolved teclmiques. 

Garcia-Vela, A., Gerber, R. B. Hybrid quantum-semiclassical wave packet method for molecular dynamics Application to photolysis of Ar...HCl. J. Chem. Phys. 98 (1993) 427-43... 

As a last example of a molecular system exhibiting nonadiabatic dynamics caused by a conical intersection, we consider a model that recently has been proposed by Seidner and Domcke to describe ultrafast cis-trans isomerization processes in unsaturated hydrocarbons [172]. Photochemical reactions of this type are known to involve large-amplitode motion on coupled potential-energy surfaces [169], thus representing another stringent test for a mixed quantum-classical description that is complementary to Models 1 and II. A number of theoretical investigations, including quantum wave-packet studies [163, 164, 172], time-resolved pump-probe spectra [164, 181], and various mixed... 

Recently, there has been much interest in the development and application of multidimensional coherent nonlinear femtosecond techniques for the study of electronic and vibrational dynamics of molecules [1], In such experiments more than two laser pulses have been used [2-4] and the combination of laser pulses in the sample creates a nonlinear polarization, which in turn radiates an electric field. The multiple laser pulses create wave packets of molecular states and establish a definite phase relationship (or coherence) between the different states. The laser pulses can create, manipulate and probe this coherence, which is strongly dependent on the molecular structure, coupling mechanisms and the molecular environment, making the technique a potentially powerful method for studies of large molecules. 

The first volume contained nine state-of-the-art chapters on fundamental aspects, on formalism, and on a variety of applications. The various discussions employ both stationary and time-dependent frameworks, with Hermitian and non-Hermitian Hamiltonian constructions. A variety of formal and computational results address themes from quantum and statistical mechanics to the detailed analysis of time evolution of material or photon wave packets, from the difficult problem of combining advanced many-electron methods with properties of field-free and field-induced resonances to the dynamics of molecular processes and coherence effects in strong electromagnetic fields and strong laser pulses, from portrayals of novel phase space approaches of quantum reactive scattering to aspects of recent developments related to quantum information processing. 

Figure 1. The creation, evolution, and detection of wave packets. The pump laser pulse pump (black) creates a coherent superposition of molecular eigenstates at t — 0 from the ground state I k,). The set of excited-state eigenstates N) in the superposition (wave packet) have different energy-phase factors, leading to nonstationary behavior (wave packet evolution). At time t = At the wave packet is projected by a probe pulse i probe (gray) onto a set of final states I kf) that act as a template for the dynamics. The time-dependent probability of being in a given final state f) is modulated by the interferences between all degenerate coherent two-photon transition amplitudes leading to that final state.

The complex coefficients AN contain both the amplitudes and initial phases of the exact molecular eigenstates N) that are prepared by the pump laser, and the En are the excited-state eigenenergies. The probe laser field interacts with the wave packet after the pump pulse is over, projecting it onto a specific final state T ) at some time delay At. This final state is the template onto which the wave packet dynamics are projected. The time dependence of the differential signal, Sf(At), for projection onto a single final state can be written as... 

Our goals were to elucidate important physical concepts in energy-angle resolved TRPES and to illustrate the range of its applicability to problems in molecular dynamics. We discussed general aspects of femtosecond pump-probe experiments from both the wave packet and the frequency domain point of view. Experimentalists are, in principle, free to choose a final state in which to observe the wave packet dynamics of interest. We emphasized the critical role of the choice of the final state in determining both the experimental technique (e.g., collection of photons or particles) and the information content of an experiment (averaged or state-resolved). The molecular ionization continuum has a rich structure that can act as a template onto which multidimensional wave packet dynamics may be projected. The set of electronic states of the cation are sensitive to both the electronic population... 

---