Selective excitation of coupled CO vibrations on a dissipative Cu(100) surface by shaped infrared laser pulses

摘要: In a previous paper [Beyvers et al., J. Chem. Phys. 124, 234706 (2006)], the possibility to mode and state selectively excite various vibrational modes of CO molecule adsorbed on dissipative Cu(100) surface by shaped IR pulses was examined. Reduced-dimensionality models with stretching-only coordinates were employed do so. This model is now extended goal include rotational modes. First, we present an analysis bound states in full dimension; i.e., six-dimensional eigenstates are obtained diagonalizing Hamiltonian containing semiempirical potential Tully al. [J. Vac. Sci. Technol. A 11, 1914 (1993)]. achieved using contracted iterative eigensolver based coupled two-term Lanczos algorithm reorthogonalization. Reduced-dimension subsystem eigenvectors also computed then used study selective excitation presence dissipation within density matrix formalism for open systems. propagations, up four degrees freedom included, namely, r (the C-O distance), Z molecule-surface phi theta azimuthal polar angles molecular axis respect surface). Short, intense laser rationally engineered further refined optimal control theory, again excitation. Also, IR-laser induced desorption studied. For calculations, two-mode (r,Z) dipole angular dependence coupling electronic refined.