Refine
Has Fulltext
- no (14)
Document Type
- Article (14) (remove)
Language
- English (14)
Is part of the Bibliography
- yes (14)
Keywords
- surface chemistry (2)
- dissipative dynamics (1)
- isotope effects (1)
- laser chemistry (1)
- photochemistry (1)
- quantum control (1)
- quantum dynamics (1)
- ultrafast reactions (1)
Institute
We present a systematic study of the influence of energy and phase relaxation on dynamic polarizability simulations in the linear response regime. The nonperturbative approach is based on explicit electron dynamics using short laser pulses of low intensities. To include environmental effects on the property calculation, we use the time- dependent configuration-interaction method in its reduced density matrix formulation. Both energy dissipation and nonlocal pure dephasing are included. The explicit treatment of time-resolved electron dynamics gives access to the phase shift between the electric field and the induced dipole moment, which can be used to define a useful uncertainty measure for the dynamic polarizability. The nonperturbative treatment is compared to perturbation theory expressions, as applied to a simple model system, the rigid H-2 molecule. It is shown that both approaches are equivalent for low field intensities, but the time-dependent treatment provides complementary information on the phase of the induced dipole moment, which allows for the definition of an uncertainty associated with the computation of the dynamic polarizability in the linear response regime.
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.
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 (i) a jellium-type and (ii) 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 (adsorption) and below (subsurface absorption) a Pd(111) 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.
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.