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

Desorption induced by single and multiple electronic transitions is describ ed by a reduced density matrix formulation in a discrete energy representat ion. The discrete energy basis is comprised of the eigenfunctions of the sy stem Hamiltonian augmented by an asymptotic potential wall, and has a numbe r of advantages over its coordinate counterpart, such as the minimization o f the basis size. The Liouville-von Neumann equation of a Lindblad semigrou p form is solved numerically using a short-time Chebyshev propagation schem e. The dynamics of NO photodesorption from metals is investigated with one- dimensional two-state models corresponding to both the Menzel-Gormer-Redhea d and Antoniewicz mechanisms. Desorption stimulated by both weak cw and str ong pulsed light sources are examined. (C) 1999 American Institute of Physi cs. [S0021-9606(99)70242-4].