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Parallel implementation of an iterative determination of energy levels of large molecular systems is presented. The basic step consists in acting the Hamiltonian operator H on a wavefunction u , and is achieved by means of a Pseudo Spectral Split Hamiltonian scheme (Leforestier et al., J. Chem. Phys. 106 (1997) 8527). The potential term evaluation V . u , which corresponds by far to the most time consuming part in the sequential code, has been distributed over all the processors. Application to the water dimer (H 2 O) 2 Vibration–Rotation spectrum shows a very good parallel efficiency up to 64 processors.

International audience; Quantum rate calculations for the H+O2→HO+OH+O2→HO+O combustion reaction, as well as for the reverse reaction, are reported. Using the DMBE IV potential energy surface, the cumulative reaction probability N0(E)N0(E) has been directly computed for total angular momentum J=0, by means of the Seideman, Manthe and Miller Lanczos-based absorbing boundary condition method [J. Chem. Phys. 96, 4412 (1992); 99, 3411 (1993)]. Special attention has been paid to the definition of the molecular basis set, and to the sensitivity of the results to the absorbing potentials used in the asymptotic regions. The N0(E) results show very good overall agreement with the coupled channel calculations of Pack et al. [J. Chem. Phys. 102, 5998 (1995)], although the highly oscillatory behavior just above threshold renders such a comparison difficult in that energy range. The behavior of the J≠0 cumulative reaction probability has been estimated from calculations using the Jz-conserving approximation for J values in the range 10–70. This allowed us to define which reference geometry should be used in the J-shifting approximation, in order to compute the cumulative reaction probability NJ(E) for any J value. By imposing conservation of the total energy within this approximation, the rate constants are shown to display better agreement with the experimental results.

International audience; We have developed a three-dimensional potential energy surface for the lowest triplet state of the Rb2He complex. A global analytic fit is provided as in the supplementary material [see supplementary material at http://dx.doi.org/10.1063/1.4709433E-JCPSA6-136-034218 for the corresponding Fortran code]. This surface is used to perform quantum scattering calculations of 4He and 3He colliding with 87Rb2 in the partial wave J = 0 at low and ultralow energies. For the heavier helium isotope, the computed vibrational relaxation probabilities show a broad and strong shape resonance for a collisional energy of 0.15 K and a narrow Feshbach resonance at about 17 K for all initial Rb2 vibrational states studied. The broad resonance corresponds to an efficient relaxation mechanism that does not occur when 3He is the colliding partner. The Feshbach resonance observed at higher collisional energy is robust with respect to the isotopic substitution. However, its effect on the vibrational relaxation mechanism is faint for both isotopes.

International audience; The X(2)Σ ground and the A(2)Π and B(2)Σ first two excited states of Li-He and Na-He are determined using high level complete active space self-consistent field-multireference configuration interaction ab initio method. The obtained potentials differ from the ones proposed by Pascale [Phys. Rev. A 28, 632 (1983)], more strongly for the ground than for the excited states. Quantum diffusion Monte Carlo studies of small Li(∗)He(n) and Na(∗)He(n) with n ≤ 5 are performed using a diatomics-in-molecule approach to model the non-pair additive interaction potential. The sensitivity of our results to the A(2)Π and B(2)Σ potentials used is assessed by an analysis of the structure and of the energetics of the clusters. For these small clusters, the physical conclusions are essentially independent of the diatomic curves employed.

International audience; The molecular dynamics with quantum transitions (MDQT) method is applied to study the fragmentation dynamics of neon clusters following vertical ionization of neutral clusters with 3 to 14 atoms. The motion of the neon atoms is treated classically, while transitions between the adiabatic electronic states of the ionic clusters are treated quantum mechanically. The potential energy surfaces are described by the diatomics-in-molecules model in a minimal basis set consisting of the effective 2p2p orbitals on each neon atom for the missing electron. The fragmentation mechanism is found to be rather explosive, with a large number of events where several atoms simultaneously dissociate. This is in contrast with evaporative atom by atom fragmentation. The dynamics are highly nonadiabatic, especially at shorter times and for the larger clusters. Initial excitation of the neutral clusters does not affect the fragmentation pattern. The influence of spin-orbit coupling is also examined and found to be small, except for the smaller size systems for which the proportion of the Ne+ fragment is increased up to 43%. From the methodological point of view, most of the usual momentum adjustment methods at hopping events are shown to induce nonconservation of the total nuclear angular momentum because of the nonzero electronic to rotation coupling in these systems. A new method for separating out this coupling and enforcing the conservation of the total nuclear momentum is proposed. It is applied here to the MDQT method of Tully but it is very general and can be applied to other surface hopping methods.

International audience; We present diffusion Monte Carlo calculations of ground states and rotationally excited states of HCN 4Hen,4Hen, using our recently developed algorithm for importance sampled rigid body diffusion Monte Carlo [Viel et al., Comput. Phys. Commun. (in press, 2001)] within the mixed frame implementation. Excited states are studied with both fixed node approximations, and the Projection Operator Imaginary Time Spectral Evolution (POITSE) method that allows nodal constraints to be circumvented. Improvements in the POITSE algorithm allow excited states of clusters with up to 80 degrees of freedom to be determined here. The results presented here show that the rotational dynamics of the HCN molecule in 4He4He clusters are very different from the behavior of heavier molecules such as SF6.SF6. Detailed analysis of ground state densities shows that the lighter HCN molecule induces negligible adiabatic following of the helium density as a result of its rotational motion. The excited state calculations show that for small numbers of 4He4He atoms the nodal structure does not correspond to that of a freely rotating molecule. Nevertheless, the POITSE calculations indicate that there is some admixture of this nodal structure in the low-lying rotational excitations. It is found that a relatively large number of 4He4He atoms are required to achieve saturation of the effective rotational constant at the experimental value, in contradistinction to the small numbers of atoms required to saturate the rotational constant for heavier molecules such as SF6SF6 and OCS.