Selective Excitation of Molecule-Surface Vibrations in H2 and D2 Dissociatively Adsorbed on Ru(0001)

• Published in: Israel journal of chemistry 2012-05, Vol.52 (5), p.438-451
• Main Authors: Füchsel, Gernot, Tremblay, Jean Christophe, Klamroth, Tillmann, Saalfrank, Peter
• Format: Article
• Language: English
• Subjects: Control theory; dissipative dynamics; Lasers; photochemistry; quantum control; surface chemistry
• ISSN: 0021-2148; 1869-5868
• DOI: 10.1002/ijch.201100097

In this contribution we report about the selective vibrational excitation of H2 and D2 on Ru(0001) as an example for nonadiabatic coupling of an open quantum system to a dissipative environment. We investigate the possibility of achieving state‐selective vibrational excitations of H2 and D2 adsorbed on a Ru(0001) surface using picosecond infrared laser pulses. The systems’ behavior is explored using pulses that are rationally designed and others that are optimized using a time‐local variant of Optimal Control Theory. The effects of dissipation on the laser‐driven dynamics are studied using the reduced‐density matrix formalism. The non‐adiabatic couplings between adsorbate and surface are computed perturbatively, for which our recently introduced state‐resolved anharmonic rate model is used. It is shown that mode‐ and state‐selective excitation can be achieved in the absence of dissipation when using optimized laser pulses. The inclusion of dissipation in the model reduces the state selectivity and the population transfer yield to highly excited states. In this case, mode activation is most effectively realized by a rational pulse of carefully chosen duration rather than by a locally optimized pulse.