TITLE

Electronically diabatic quantum dynamics of molecular desorption

AUTHOR(S)
Beksˇic, Dario; Micha, David A.
PUB. DATE
September 1995
SOURCE
Journal of Chemical Physics;9/1/1995, Vol. 103 Issue 9, p3795
SOURCE TYPE
Academic Journal
DOC. TYPE
Article
ABSTRACT
The photodesorption of a diatomic from a metal surface, following absorption of visible or UV light, involves electronic transitions of the desorbing species coupled to the lattice vibrations and electron–hole excitations of the substrate. We present a general treatment of these phenomena, based on the Liouville–Von Neuman equation for the density operator, and a stochastic theory of localized perturbations in an extended system. The Hamiltonian of the extended molecular system is divided into a term for the localized primary degrees of freedom (DFs) affected by the desorption, coupled to secondary DFs that acts as a time-evolving bath. A self-consistent field treatment gives an effective (non-Hermitian) Hamiltonian for the primary DFs that accounts for energy fluctuation and dissipation in terms of the properties of adsorbate and substrate. A diabatic electronic representation is used to eliminate momentum couplings between adsorbate electronic states. The bath dynamics is studied for lattice vibrations and for electronic excitations. Electron–hole excitations of the substrate are considered for intraband and interband transitions. The assumption of Brownian motion leads to expressions for the dissipative potentials in terms of the time-correlation functions of lattice displacements and of electron density fluctuations. The dissipation depends on time, allowing for time-dependent substrate temperatures and generalizing the Langevin description. Dissipation contributes to the time evolution of both ground and excited electronic states of the desorbing species. The model is discussed for the special case of Ni(001)(ads)CO. © 1995 American Institute of Physics.
ACCESSION #
7647267

 

Related Articles

  • Lattice models for dipolar adsorption at metal/electrolyte interfaces using Bethe approximation. Saradha, R.; Sangaranarayanan, M. V. // Journal of Chemical Physics;9/8/1996, Vol. 105 Issue 10, p4284 

    A two-dimensional lattice model for adsorption of solvent molecules at a metal/electrolyte interface is proposed assuming two configurational states for dipoles. The generalized Ising Hamiltonian incorporating Coulombic effects and nonelectrostatic metal–solvent interaction energies is...

  • The Heisenberg antiferromagnet on the square-kagomé lattice. Richter, J.; Schulenburg, J.; Tomczak, P.; Schmalfuß, D. // Condensed Matter Physics;Sep2009, Vol. 12 Issue 3, p507 

    We discuss the ground state, the low-lying excitations as well as high-field thermodynamics of the Heisenberg antiferromagnet on the two-dimensional square-kagomé lattice. This magnetic system belongs to the class of highly frustrated spin systems with an infinite non-trivial degeneracy of...

  • Addition by subtraction in coupled cluster theory. II. Equation-of-motion coupled cluster method for excited, ionized, and electron-attached states based on the nCC ground state wave function. Musiał, Monika; Bartlett, Rodney J. // Journal of Chemical Physics;7/14/2007, Vol. 127 Issue 2, p024106 

    New iterative double and triple excitation corrections to the equation-of-motion coupled cluster (EOM-CC) based upon the recently developed nCC methods [Bartlett and Musiał, J. Chem. Phys. 125, 204105–1 (2006)] are applied to excitation energies (EEs), ionization potentials (IPs), and...

  • Excitation energy transfer efficiency: Equivalence of transient and stationary setting and the absence of non-Markovian effects. Jesenko, Simon; Zˇnidaricˇ, Marko // Journal of Chemical Physics;May2013, Vol. 138 Issue 17, p174103 

    We analyze efficiency of excitation energy transfer in photosynthetic complexes in transient and stationary setting. In the transient setting, the absorption process is modeled as an individual event resulting in a subsequent relaxation dynamics. In the stationary setting the absorption is a...

  • Intramolecular excitations in the H[sub 2]O..CO complex studied by diffusion Monte Carlo and ab... Sandler, P.; Sadlej, J. // Journal of Chemical Physics;10/1/1997, Vol. 107 Issue 13, p5022 

    Focuses on intramolecular excitation frequencies or frequency shifts in molecular complexes. Formation of a weak bond; Changes in molecular vibration frequencies due to coupling between inter- and intramolecular degrees of freedom; Treatment of all degrees of freedom in full microscopic detail;...

  • Adsorption Sites of Hydrogen Atomon Pure and Mg-Doped Multi-Walled Carbon Nanotubes. Al-Ghamdi, A. A.; Shalaan, E.; Al-Hazmi, F. S.; Faidah, Adel S.; Al-Heniti, S.; Husain, M. // Journal of Nanomaterials;2012, p1 

    Hydrogen adsorption sites on pure multiwalled carbon nanotube (MWCNT) and Mg-dopedMWCNTs material system have been investigated using molecular dynamics (MD) simulations as well as quantum chemical calculations. Through combiningMWCNTs with Mg, the hydrogen adsorption sites energy on this...

  • Revealing novel quantum phases in quantum antiferromagnets on random lattices. Yu, R.; Haas, S.; Roscilde, T. // Condensed Matter Physics;Sep2009, Vol. 12 Issue 3, p519 

    Quantum magnets represent an ideal playground for the controlled realization of novel quantum phases and of quantum phase transitions. The Hamiltonian of the system can be indeed manipulated by applying a magnetic field or pressure on the sample. When doping the system with non-magnetic...

  • Excited light meson spectroscopy from lattice QCD. Thomas, Christopher E.; Hadron Spectrum Collaboration // AIP Conference Proceedings;4/19/2012, Vol. 1441 Issue 1, p310 

    I report on recent progress in calculating excited meson spectra using lattice QCD. With novel techniques we can now extract extensive spectra of excited mesons with high statistical precision, including spin-four states and those with exotic quantum numbers. I review a new calculation of a...

  • Parallel transport in an entangled ring. Wootters, William K. // Journal of Mathematical Physics;Sep2002, Vol. 43 Issue 9, p4307 

    This article defines a notion of parallel transport in a lattice of quantum particles, such that the transformation associated with each link of the lattice is determined by the quantum state of the two particles joined by that link. We focus particularly on a one-dimensional lattice—a...

Share

Read the Article

Courtesy of VIRGINIA BEACH PUBLIC LIBRARY AND SYSTEM

Sorry, but this item is not currently available from your library.

Try another library?
Sign out of this library

Other Topics