Electronic energy flow in an isolated molecular system involves coupling between the electronic and nuclear subsystems, and the coupled system evolves to a statistical mixture of pure states. In semiclassical theories, nuclear motion is treated using classical mechanics, and electronic motion is treated as an open quantal system coupled to a "bath" of nuclear coordinates. We have previously shown how this can be simulated by a time-dependent Schrödinger equation with coherent switching and decay of mixing, where the decay of mixing terms model the dissipative effect of the environment on the electronic subdynamics (i.e., on the reduced dynamics of the electronic subsystem). In the present paper we reformulate the problem as a Liouville-von Neumann equation of motion (i.e., we propagate the reduced density matrix of the electronic subsystem), and we introduce the assumption of first-order linear decay. We specifically examine the cases of equal relaxation times for both longitudinal (i.e., population) decay and transverse decay (i.e., dephasing) and of longitudinal relaxation only, yielding the linear decay of mixing (LDM) and the population-driven decay of mixing (PDDM) schemes, respectively. Because we do not generally know the basis in which coherence decays, that is, the pointer basis, we judge the semiclassical methods in part by their ability to give good results in both the adiabatic and diabatic bases. The accuracy in the prediction of physical observables is shown to be robust not only with respect to basis but also with respect to the way in which demixing is incorporated into the master equation for the density matrix. The success of the PDDM scheme is particularly interesting because it incorporates the least amount of decoherence (i.e., the PDDM scheme is the most similar of the methods discussed to the fully coherent semiclassical Ehrenfest method). For both the new and previous decay of mixing schemes, four kinds of decoherent state switching algorithms are analyzed and compared to one another:  natural switching (NS), self-consistent switching (SCS), coherent switching (CS), and globally coherent switching (GCS). The CS formulations are examples of a non-Markovian method, in which the system retains some memory of its history, whereas the GCS, SCS, and NS schemes are Markovian (time local). These methods are tested against accurate quantum mechanical results using 17 multidimensional atom-diatom test cases. The test cases include avoided crossings, conical interactions, and systems with noncrossing diabatic potential energy surfaces. The CS switching algorithm, in which the state populations are controlled by a coherent stochastic algorithm for each complete passage through a strong interaction region, but successive strong-interaction regions are not mutually coherent, is shown to be the most accurate of the switching algorithms tested for the LDM and PDDM methods as well as for the previous decay of mixing methods, which are reformulated here as Liouville-von Neumann equations with nonlinear deca...

Metal nanoparticles are important in several emerging technologies, but their size-selected thermodynamic properties are hard to obtain from experiment. We have characterized the energetic and structural properties of unsupported neutral Aln (2

State-to-state, state-specific, and cumulative reaction probabilities are presented for the bimolecular scattering process Li + HF → H + LiF in the ground electronic state. Calculations were performed for zero total angular momentum at total energies from 0.26 to 0.50 eV (relative to HF at its classical equilibrium bond distance and infinitely far from Li). The energy dependence of the state-to-state, initial-state-selected, and cumulative reaction probabilities for LiFH in the low-energy regime displays a pronounced resonance structure due to quasibound states associated with a Li···FH van der Waals well in the entrance valley of the potential energy surface. The lifetimes of the long-lived resonances are obtained by fitting the calculated eigenphase sum to the multichannel Breit−Wigner formula. The final rotational state distributions of the LiF product fragment resulting from decay of the resonance state complexes are presented for two resonances. Quantum numbers are assigned to the resonances using bound-state and quasibound-state calculations in the Li···FH van der Waals well, and possible decay mechanisms are discussed. The lifetimes show a systematic dependence on the translational vibrational quantum number.