Dissipative quantum dynamics in discrete energy representation: Photon-stimulated desorption of NO from metals

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Articles you may be interested inThe surface temperature dependence of the inelastic scattering and dissociation of hydrogen molecules from metal surfaces Surface temperature dependence of rotational excitation of H 2 scattered from Pd(111) J. Chem. Phys. 111, 9791 (1999); 10.1063/1.480315 Ten-dimensional wave packet simulations of methane scatteringThe scattering dynamics of vibrationally excited NO from a metal surface is investigated theoretically using a dissipative model that includes both the neutral and negative ion states. The Liouville-von Neumann equation is solved numerically by a Monte Carlo wave packet method, in which the wave packet is allowed to ''jump'' between the neutral and negative ion states in a stochastic fashion. It is shown that the temporary population of the negative ion state results in significant changes in vibrational dynamics, which eventually lead to vibrationally inelastic scattering of NO. Reasonable agreement with experiment is obtained with empirical potential energy surfaces. In particular, the experimentally observed facile multiquantum relaxation of the vibrationally highly excited NO is reproduced. The simulation also provides interesting insight into the scattering dynamics.

Section: B Liouville-von Neumann Equationmentioning

confidence: 99%

Monte Carlo wave packet study of negative ion mediated vibrationally inelastic scattering of NO from the metal surface

Guo

2002

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“…This is different from recent work were continua have been treated with particle-in-a-box type eigenstate representations. 12,29 In Fig. 2 we show, as a measure of the system-bath coupling strength as a function of the distance from the surface, the energy loss rate Ϫd͗Ĥ S ͘/dt.…”

Section: Nonlinear System-bath Couplingmentioning

confidence: 99%

Open-system quantum dynamics for gas-surface scattering: Nonlinear dissipation and mapped Fourier grid methods

Nest

Saalfrank

2000

“…[5][6][7] Many theoretical works on this system have been done. [8][9][10][11][12][13][14][15][16][17] The Menzel-Gomer-Redhead ͑MGR͒ model 18,19 and the Antoniewicz model 20 have been proposed as the two major mechanisms of the PSD process, with the latter being adopted in most works and with quantum wave packet, time-dependent perturbation theory, and density matrix also being used. Both the MGR and Antoniewicz models are supported by simple electronic structure calculations.…”

Section: Introductionmentioning

confidence: 99%

Effects of vibrational relaxation on the photodesorption of NO from Pt(111): A density matrix study

Abe

Yamashita

2003

Articles you may be interested inOptimal control of open quantum systems: A combined surrogate Hamiltonian optimal control theory approach applied to photochemistry on surfaces Photodesorption of physisorbed molecules from a Ag(111) surface: The low photon energy threshold and the low translational temperature of desorbed molecules J. Chem. Phys. 108, 7775 (1998); 10.1063/1.476213 Two-dimensional wave packet studies of photon-stimulated desorption of NO from a metal surface induced by single and multiple electronic excitationsThe effect of vibrational relaxation on the photodesorption dynamics of NO from a Pt͑111͒ surface has been investigated theoretically. Although this system has been studied in many previous works, the relaxation of NO stretching vibration due to the interaction with electron-hole pairs in metals has not been included in conventional models. Although the relaxation lifetimes of the first-excited vibrational state of diatomic molecules adsorbed on metal surfaces are generally in the range 0.1-1 ps, the desorption dynamics of NO is complete in about 1 ps. Therefore, it is considered that the vibrational relaxation can influence the vibrational state of this stretching mode during the desorption process. We described the desorption dynamics by using the time propagation of the density matrix. The effects of vibrational relaxation were included by using a Redfield-type model. We also investigated the validity of the parameters for dynamical calculations by ab initio methods. As a result, we obtained physically reasonable results for the desorption probability, mean translational energy, and vibrational state distribution for the desorbed NO molecules.