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

Tremblay, Jean Christophe; Beyvers, Stephanie; Saalfrank, Peter

doi:10.1063/1.2916710

Cited by 28 publications

(17 citation statements)

References 86 publications

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“…The time evolution of the reduced density operator, ͑t͒, obeys the Liouville-von Neumann equation. 26 By ͑i͒ expressing the density operator in the basis of the vibrational eigenstates n = ͉n͘ of the vibrating H atom, ͑ii͒ using the semiclassical dipole approximation to treat the coupling of these vibrations to an external field, and ͑iii͒ employing socalled Lindblad operators 27 to enforce environment-induced, dissipative transitions between the vibrational levels with rates ⌫ n→n Ј , the time evolution of the reduced density matrix elements becomes 22,28,29 …”

Section: B Dynamical Simulationsmentioning

confidence: 99%

Electronic damping of anharmonic adsorbate vibrations at metallic surfaces

2010

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The nonadiabatic coupling of an adsorbate close to a metallic surface leads to electronic damping of adsorbate vibrations and line broadening in vibrational spectroscopy. Here, a perturbative treatment of the electronic contribution to the lifetime broadening serves as a building block for a new approach, in which anharmonic vibrational transition rates are calculated from a position-dependent coupling function. Different models for the coupling function will be tested, all related to embedding theory. The first two are models based on a scattering approach with ͑i͒ a jellium-type and ͑ii͒ a density functional theory based embedding density, respectively. In a third variant a further refined model is used for the embedding density, and a semiempirical approach is taken in which a scaling factor is chosen to match harmonic, single-site, first-principles transition rates, obtained from periodic density functional theory. For the example of hydrogen atoms on ͑adsorption͒ and below ͑subsurface absorption͒ a Pd͑111͒ surface, lifetimes of and transition rates between vibrational levels are computed. The transition rates emerging from different models serve as input for the selective subsurface adsorption of hydrogen in palladium starting from an adsorption site, by using sequences of infrared laser pulses in a laser distillation scheme.

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Section: B Dynamical Simulationsmentioning

confidence: 99%

Electronic damping of anharmonic adsorbate vibrations at metallic surfaces

2010

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“…In this basis and in the interaction picture, 36 the time evolution of the reduced density operator, when expressed in Lindblad form, 19,[36][37][38][39][40][41] is given by…”

Section: B Reduced Density Matrix Formalismmentioning

confidence: 99%

Selective subsurface absorption of hydrogen in palladium using laser distillation

Tremblay

Saalfrank

2009

The Journal of Chemical Physics

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A theoretical model for the selective subsurface absorption of atomic hydrogen in a Pd(111) surface by infrared (IR) laser pulses is presented. The dynamics of the adsorbate is studied within the reduced density matrix approach. Energy and phase relaxation of the hydrogen atom are treated using the semigroup formalism. The vibrational excitation leading to subsurface absorption is performed using rationally designed pulses as well as IR laser pulses optimized on-the-fly. It is shown that dissipation can be used as a tool to transfer population to an otherwise inaccessible state via a mechanism known as "laser distillation." We demonstrate that when the reaction path is generalized from a reduced one-dimensional to full three-dimensional treatment of the system, the laser control strategy can prove very different.

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“…To treat energy dissipation due to nonadiabatic coupling, lowering and raising operators are used 50,56À60…”

Section: ' Theorymentioning

confidence: 99%

The Effects of Electron–Hole Pair Coupling on the Infrared Laser-Controlled Vibrational Excitation of NO on Au(111)

2011

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In this work, we present theoretical simulations of laser-driven vibrational control of NO adsorbed on a gold surface. Our goal is to tailor laser pulses to selectively excite specific modes and vibrational eigenstates, as well as to favor photodesorption of the adsorbed molecule. To this end, various control schemes and algorithms are applied. For adsorbates at metallic surfaces, the creation of electron-hole pairs in the substrate is known to play a dominant role in the transfer of energy from the system to the surroundings. These nonadiabatic couplings are included perturbatively in our reduced density matrix simulations using a generalization of the state-resolved position-dependent anharmonic rate model we recently introduced. An extension of the reduced density matrix is also proposed to provide a sound model for photodesorption in dissipative systems.

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

Cited by 28 publications

References 86 publications

Electronic damping of anharmonic adsorbate vibrations at metallic surfaces

Electronic damping of anharmonic adsorbate vibrations at metallic surfaces

Selective subsurface absorption of hydrogen in palladium using laser distillation

The Effects of Electron–Hole Pair Coupling on the Infrared Laser-Controlled Vibrational Excitation of NO on Au(111)

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