Nonadiabatic effects in the H+H_2 exchange reaction: accurate quantum dynamics calculations at a state-to-state level

Real wave packet propagations were carried out on both a single ground electronic state and two-coupled-electronic states of the title reaction to investigate the extent of nonadiabatic effects on the distinguishable-atom reaction cross sections. The latest diabatic potential matrix of Abrol and Kuppermann [J. Chem. Phys. 116, 1035 (2002)] was employed in the present nonadiabatic quantum state-to-state scattering calculations over a total energy range-from threshold (the zero point of the reagent H_2) to 3.0 eV. Based on the assumption that the hydrogen atoms are distinguishable in the collisions where the inelastic and elastic ones are excluded, no significant nonadiabatic effects have been found in the calculations of the full state-to-state integral and differential cross sections up to a total energy of 3.0 eV for product vibrational levels v' = 0, 1, 2, 3. Our results therefore confirm the recent and the previous studies of the geometric phase effects in H+H_2 employing a different diabatic double many-body expansion potential matrix or a different BKMP2 potential energy surface

Scattering solutions of the spinless Salpeter equation

A method to compute the scattering solutions of a spinless Salpeter equation (or a Schrodinger equation) with a central interaction is presented. This method relies on the 3-dimensional Fourier grid Hamiltonian method used to compute bound states. It requires only the evaluation of the potential at equally spaced grid points and yields the radial part of the scattering solution at the same grid points. It can be easily extended to the case of coupled channel equations and to the case of non-local interactions.Comment: 7 page

Coriolis coupling effects in the calculation of state-to-state integral and differential cross sections for the H+D-2 reaction

The quantum wavepacket parallel computational code DIFFREALWAVE is used to calculate state-to-state integral and differential cross sections for the title reaction on the BKMP2 surface in the total energy range of 0.4-1.2 eV with D-2 initially in its ground vibrational-rotational state. The role of Coriolis couplings in the state-to-state quantum calculations is examined in detail. Comparison of the results from calculations including the full Coriolis coupling and those using the centrifugal sudden approximation demonstrates that both the energy dependence and the angular dependence of the calculated cross sections are extremely sensitive to the Coriolis coupling, thus emphasizing the importance of including it correctly in an accurate state-to-state calculation. (c) 2007 American Institute of Physics

Quantum reactive scattering calculations of cross sections and rate constants for the N(2D) + O2(X3Σg-) → O(3Π) + NO(X2Π) reaction

Time-dependent quantum wavepacket calculations have been performed on the two lowest adiabatic potential energy surfaces (2 2A´ and 1 2A˝) for the N(2D) + O2(X3Σg-) → O(3Π) + NO(X2Π) reaction. The calculations have been carried out, on these recently published potential energy surfaces, using the real wavepacket method together with a new dispersion fitted finite difference technique for evaluating the action of the radial kinetic energy operator. Reaction probabilities, corresponding to the O2 reactant in its ground vibrational-rotational state, have been calculated for both surfaces and for many different values of the total angular momentum quantum number (J), within the helicity decoupling approximation. The reaction probabilities associated with all other relevant J values have been interpolated, and to a smaller extent extrapolated, using a capture model, to yield probabilities as a function of energy. The probabilities have in turn been summed to yield energy dependent cross sections and then used to compute rate constants. These rate constants are compared with ones obtained from quasiclassical trajectory (QCT) and variational transition state theory (VTST) calculations performed on the same surfaces. There is a good agreement between the wavepacket and QCT cross sections for reaction on both potential energy surfaces considered, with the exception of the near threshold region, where the reaction probability is dominated by tunnelling. Comparison of the predicted rate constants shows that for the 2 2A´ surface, above 300 K, the wavepacket, QCT and VTST results are quite similar. For the 1 2A˝ surface, however, significant differences occur between the wavepacket and the other methods. These differences become smaller with increasing temperature. It is likely that these differences arise, at least in part, from the fact that, when calculating the rate constants, the reactants are restricted to be in their lowest vibrational-rotational state in the wavepacket calculations but are selected from a thermally equilibrated population in the other methods

Quantum dynamical study of the O(1D)+HCl reaction employing three electronic state potential energy surfaces

Quantum dynamical calculations are reported for the title reaction, for both product arrangement channels and using potential energy surfaces corresponding to the three electronic states, 1 (1)A('), 2 (1)A('), and 1 (1)A('), which correlate with both reactants and products. The calculations have been performed for J=0 using the time-dependent real wavepacket approach by Gray and Balint-Kurti [J. Chem. Phys. 108, 950 (1998)]. Reaction probabilities for both product arrangement channels on all three potential energy surfaces are presented for total energies between 0.1 and 1.1 eV. Product vibrational state distributions at two total energies, 0.522 and 0.722 eV, are also presented for both channels and all three electronic states. Product rotational quantum state distributions are presented for both product arrangement channels and all three electronic states for the first six product vibrational states. (c) 2008 American Institute of Physics

Memorial Viewpoint for Joop van Lenthe

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