Dissociative chemisorption of H2 on the Cu(110) surface: A quantum and quasiclassical dynamical study.

Six-dimensional quantum dynamical and quasiclassical trajectory (QCT) calculations are reported for the reaction and vibrationally inelastic scattering of (v=0,1,j=0) H2 scattering from Cu(110), and for the reaction and rovibrationally elastic and inelastic scattering of (v=1,j=1) H2 scattering from Cu(110). The dynamics results were obtained using a potential energy surface obtained with density functional theory using the PW91 functional. The reaction probabilities computed with quantum dynamics for (v=0,1,j=0) were in excellent agreement with the QCT results obtained earlier for these states, thereby validating the QCT approach to sticking of hydrogen on Cu(110). The vibrational de-excitation probability P(v=1,j=0→v=0) computed with the QCT method is in remarkably good agreement with the quantum dynamical results for normal incidence energies En between 0.2 and 0.6 eV. The QCT result for the vibrational excitation probability P(v=0,j=0→v=1) is likewise accurate for En between 0.8 and 1 eV, but the QCT method overestimates vibrational excitation for lower En. The QCT method gives probabilities for rovibrationally (in)elastic scattering, P(v=1,j=1→v′,j′), which are in remarkably good agreement with quantum dynamical results. The rotationally averaged, initial vibrational state-selective reaction probability obtained with QCT agrees well with the initial vibrational state-selective reaction probability extracted from molecular beam experiments for v=1, for the range of collision energies for which the v=1 contribution to the measured total sticking probability dominates. The quantum dynamical probabilities for rovibrationally elastic scattering of (v=1,j=1) H2 from Cu(110) are in good agreement with experiment for En between 0.08 and 0.25 eV. [ABSTRACT FROM AUTHOR]