title: Surface femtochemistry: observation and quantum control of frustrated desorption of alkali atoms from noble metals.
abstract: This review presents a case study of the direct, real-time observation of a surface photochemical reaction, namely the frustrated photodesorption of alkali atoms from noble metal surfaces. Charge transfer excitation of an electron from the metal substrate into an unoccupied resonance of the alkali atom instantaneously turns on the repulsive Coulomb force inducing the nuclear motion of both the adsorbate and substrate atoms. The incipient nuclear wave packet dynamics are documented for the case of Cs/Cu(111) through the accompanying change in the surface electronic structure. The intimate view of atoms attempting to escape the surface bond highlights the unique role of the substrate in the electronic and nuclear dynamics that ultimately determine the product yields. Moreover, slow dephasing of the coherent polarization is exploited to demonstrate the control of nuclear wave packets through the phase of the excitation light.
authors.affiliation: Department of Physics and Astronomy, University of Pittsburgh, Pittsburgh, Pennsylvania 15260, USA. petek@pitt.edu
authors.forename: Hrvoje
authors.initials: H
authors.lastname: Petek
authors.forename: Susumu
authors.initials: S
authors.lastname: Ogawa