Stereodynamics of the Ca + HCl → CaCl + H molecular reaction imposed by the rotational-excited states of HCl

The effects of the initial rotational-excited states of the HCl molecule on the stereodynamics properties of the Ca + HCl molecular reaction are investigated using the quasiclassical trajectory theory and the analytical potential energy surface. The orientation and alignment behaviors for the rotational angular momentum of the product, along with the generalized differential cross section (PDDCS)-dependent polarization, are calculated to explore the stereodynamics properties. The initial rotational-excited states of the HCl molecule impose a remarkable effect on the vector correlation distributions, regardless of the orientation, alignment, or PDDCS. The forward, backward, and weak sideway scatterings are found in the Ca + HCl → CaCl + H molecular reaction. The results demonstrate that the initial rotational-excited state of j = 3 results in more obvious stereodynamics effects.     

Quantum dynamics of dissociative adsorption of H_2 and D_2:The time-dependent wave packet method

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Evaluation of molecular integral of Cartesian Gaussian type basis function with complex‐valued center coordinates and exponent via the McMurchie–Davidson recursion formula,and its application to electron dynamics

McMurchie–Davidson recursion formula is extended to derive the ab initio molecular integrals with higher angular quantum number complex Gaussian type basis function which has complex‐valued center coordinates and a complex‐valued exponent. Using the analytical recursion formulae, some calculations of electronic dynamics after beta decay of tritium hydride molecular ion HT⁺ are performed by a quantum wave packet method with thawed Gaussian basis functions of s‐ and p‐type. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2009     

Reactive chemical dynamics through conical intersections

Reaction dynamics of prototypical, D + H₂ and Cl (²P) + H₂, chemical reactions occurring through the conical intersections of the respective coupled multi-sheeted potential energy surfaces is examined here. In addition to the electronic coupling, nonadiabatic effects due to relativistic spin-orbit coupling are also considered for the latter reaction. A time-dependent wave packet propagation approach is undertaken and the quantum dynamical observables viz., energy resolved reaction probabilities, integral reaction cross-sections and thermal rate constants are reported.     

Nonadiabatic quantum dynamics in O(3P)+H2→OH+H: a revisited study

To investigate the extent of nonadiabatic effects in the title reaction, quasi-classical trajectory and nonadiabatic quantum scattering as well as the nonadiabatic quantum-classical trajectory calculations were performed on the accurate ab initio benchmark potential energy surfaces of the lowest (3)A' and (3)A\" electronic states [Rogers et al., J Phys Chem A 2000, 104, 2308], together with the spin-orbit coupling matrix [Maiti and Schatz, J Chem Phys 2003, 119, 12360] and the lowest singlet (1) A' potential energy surface [Dobby and Knowles, Faraday Discuss 1998, 110, 247]. Comparison of the calculated total cross sections from both adiabatic and nonadiabatic calculations has demonstrated that for adiabatic channels including (3)A'→(3)A' and (3)A\"→(3)A\", difference does exist between the two kinds of adiabatic and nonadiabatic calculations, showing nonadiabatic effects to some extent. Such nonadiabatic effects tend to become more conspicuous at high collision energies and are found to be more pronounced with trajectories/quantum wave packet initiated on (3)A' than on (3)A\". Furthermore, the present study also showed that nonadiabatic effects can bring the component of forward-scattering in the product angular distributions.