Quantum dynamics of finite atomic and molecular systems through density matrix methods

We develop a mixed quantum-classical formulation to describe the dynamics of few- and many-body atomic systems by applying a partial Wigner transform over the quantum Liouville equation of motion. In this approach, the density operator becomes a function in quasiclassical phase space, while remaining an operator over a subset of quantal variables. By taking appropriate limits and introducing an effective potential, we derive equations of motion describing quasiclassical nuclear trajectories coupled to quantal electronic evolution. We also introduce a variable timestep procedure to account for the disparity between slow nuclear motion and fast electronic fluctuations.; Our mixed quantum-classical method is applied to the study of three simple one-dimensional two-state models. The first model represents the photoinduced desorption of an alkali atom from a metal surface, where near-resonant electron transfer is important. A second model explores a binary collision under conditions where two avoided crossings are present. The third model follows the photoinduced dissociation of the sodium iodide complex, whose long-range attractive surface results in oscillations of internuclear distance. Quantities such as state populations and quantum coherence are computed, and found to be in excellent agreement with precise quantal results obtained through fast Fourier transform grid methods.; Having validated our approach, we turn to the study of alkali atoms embedded in rare gas clusters, treating the alkali atom-rare gas interactions with l-dependent semi-local pseudopotentials. Light emission from the electronic motion of the alkali atom is derived in the semiclassical limit, and computational methods to render the simulation feasible for a many-atom cluster are discussed. The formalism is applied to lithium atoms in helium clusters, where the cluster configuration and the electronic population dynamics of the lithium atom are monitored over time. We study both the ground and first excited states of lithium, and introduce a resonant electromagnetic field to induce electronic transitions. Our results correlate well with other experimental and theoretical studies on doped helium droplets, and provide insight into the dynamics of an excited lithium atom near a helium cluster surface.