Selective excitation of molecule-surface vibrations in H2 and D2 dissociatively adsorbed on Ru(0001)
- 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 toIn 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.…
Author details: | Gernot FüchselORCiD, Jean Christophe TremblayORCiDGND, Tillmann KlamrothORCiDGND, Peter SaalfrankORCiDGND |
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DOI: | https://doi.org/10.1002/ijch.201100097 |
ISSN: | 0021-2148 |
Title of parent work (English): | Israel journal of chemistry |
Publisher: | Wiley-VCH |
Place of publishing: | Weinheim |
Publication type: | Article |
Language: | English |
Year of first publication: | 2012 |
Publication year: | 2012 |
Release date: | 2017/03/26 |
Tag: | dissipative dynamics; photochemistry; quantum control; surface chemistry |
Volume: | 52 |
Issue: | 5 |
Number of pages: | 14 |
First page: | 438 |
Last Page: | 451 |
Funding institution: | Deutsche Forschungsgemeinschaft [Sa547/8-1] |
Organizational units: | Mathematisch-Naturwissenschaftliche Fakultät / Institut für Chemie |
Peer review: | Referiert |