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International Laser Science Conference

Theory of an infrared irradiated adbond

Sander van Smaalen, Thomas F. George

Published Jan 1, 1986• 0 citations
Publisher

Abstract

The dynamics of an adsorbed atom irradiated by an infrared laser in resonance with the vibrational levels of the adbond can be described by the reduced density matrix of the adbond. A nonperturbative approach for the laser-adbond interaction is presented. Relaxation against the substrate degrees of freedom is described by second-order perturbation theory. Both pulsed lasers and cw lasers are considered. Expressions for the transition probabilities are derived in the low-intensity and in the high-intensity limits. It appears that the time evolution of the occupation probabilities is coupled to those of the coherences, i.e., a master equation cannot be obtained. The time evolution of all the elements of the reduced density matrix has to be taken into account. These expressions act as a basis for the study of physical processes as resonant de sorption, resonant heating, and laser-induced thermal desorption. Resonant desorption is described by the addition of loss terms into the equations of motion of the occupation probabilities. Expressions for the rate of desorption as well as the rate of energy transfer to the substrate are given. In particular, a comparison is made for the effect of a cw laser vs a pulsed laser on the desorption and resonant heating.

DOI
10.1364/ils.1986.thl37

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Physical review. B, Condensed matter•Jan 1, 1987•6 citations
The dynamics of an adsorbed atom irradiated by an infrared laser in resonance with the vibrational levels of the adbond can be described by the reduced density matrix of the adbond. A nonperturbative approach for the laser-adbond interaction is presented. Relaxation against the substrate degrees of freedom is described by second-order perturbation theory. Both pulsed lasers and cw lasers are considered. Expressions for the transition probabilities are derived in the low-intensity and in the high-intensity limits. It appears that the time evolution of the occupation probabilities is coupled to those of the coherences, i.e., a master equation cannot be obtained. The time evolution of all the elements of the reduced density matrix has to be taken into account. These expressions act as a basis for the study of physical processes as resonant de sorption, resonant heating, and laser-induced thermal desorption. Resonant desorption is described by the addition of loss terms into the equations of motion of the occupation probabilities. Expressions for the rate of desorption as well as the rate of energy transfer to the substrate are given. In particular, a comparison is made for the effect of a cw laser vs a pulsed laser on the desorption and resonant heating.
The irradiation by infrared laser light of an atom adsorbed on the surface of a harmonic crystal is considered. The dynamic coupling between the atom (its motion) and the substrate degrees of freedom (phonon field) in the presence of a confining potential well (van der Waals bond between atom and crystal) gives rise to thermal relaxation of this adbond configuration. Both the atom and the substrate are assumed to be transparent, but the bond is allowed to have non-vanishing dipole-moment matrix elements, which couple the external field to the adsorbate. The equation of motion for the reduced adbond density operator is obtained with reservoir theory, and the relaxation constants are expressed in properties of the crystal. With a similar method, the spectral profile for absorption of weak radiation is derived. Subsequently, the illumination by a strong finite-linewidth laser field which is in close resonance with a single transition of the adbond is examined. The optical Bloch equations in operator form are derived and applied to study the process of laser heating of the crystal. It is pointed out how this mechanism can be understood as resulting from (multi)photon-phonon conversion reactions which are mediated by the adbond.
Adsorbed atoms on the surface of a harmonic lattice are immersed in a strong laser field. The optical Bloch equations are derived, which include the thermal relaxation and the coherent excitation of the adbond. This is accomplished by a transformation to dressed states, which diagonalizes the interaction with the laser. The single-phonon couplings are then understood as transitions between dressed states. The radiative contributions for arbitrarily strong fields are obtained in the master equation, and it is shown that the coherences with respect to the dressed states decay exponentially, due to the phonon relaxation. General properties of the competing phonon-induced redistribution and optical excitation of the level populations are presented, and exemplified by an explicit elaboration of a three-level system. The results are amenable to analytical evaluation once the interaction potential is prescribed, and extensions of the approach to include multiphonon processes are straightforward.
Adsorbed species on a solid-state surface interact with the large number of substrate modes, which gives rise to thermal relaxation. Commonly, the temporal evolution of the quantum state of the adsorbate is described by a master equation for the level populations (vibrational bond, internal modes, etc). It is pointed out that this approach does not necessarily give a correct account of the coupling to the solid when the effective level widths become comparable to the level separations, or larger. It is shown that the evolution of the populations does not decouple any more from the time evolution of the coherences (off-diagonal matrix elements), which implies that a random-phase approximation cannot be justified, and that the density matrix of the adsorbate is not determined only by the golden-rule transition constants. Especially, the line profiles turn out to be very sensitive to the coherence-coherence couplings. Although the coherences vanish in thermal equilibrium, their time-regression operator, and hence their mutual couplings and their couplings to the populations, which determine the absorption profile, do not. This information is lost in a master-equation treatment of relaxation.
The problem of resonant interaction between an electromagnetic radiation field and a vibronic system, such as a molecule or a localized electronphonon system, is considered. The vibronic coupling is assumed to result from displaced and distorted potential energy surfaces for the vibrational motion in the electronic quantum states involved in the resonant interaction with the radiation field. Furthermore, the vibrational energy relaxation is taken into account without assumptions about Markovian-type relaxation. In order to study correlation properties of higher than second order in the electric field strength of the light emitted a method of calculation of the expectation value of an arbitrary product combination of effective time evolution operators of the vibronic system is developed. The calculations are performed by utilizing Feynman's disentangling and operator ordering techniques and yield closed solutions in the low-temperature limit. The theory is used for studying the intensity and the normally ordered intensity correlation function of the resonance fluorescence light from a two-atom molecule excited by a relatively weak laser field, which undergoes phase fluctuations. It is shown that the vibronic coupling can give rise to an anticorrelation effect which is substantially stronger than in the case of resonance fluorescence from an atom. For the case of small vibrational damping a general formula which directly connects the asymptotic long-time behaviour of the normalized intensity correlation function with the vibrational relaxation in the molecule is deduced. It should be convenient for the determination of very small vibrational decay rates.
A coated surface of a crystal is irradiated by intense infrared light. The optically active atomic bonds absorb photons from the laser field, and the subsequent spontaneous decay goes together with emissions of phonons into the crystal. This photon phonon conversion results in an energy flux into the crystal. An equation for this flux is derived from the master equation for the level populations of the dressed atomic states. The saturation limit is discussed, and the general theory is illustrated with two examples. Furthermore, it is outlined with qualitative arguments that quantum yield of photodesorption is not sensitive to the laser power. Keywords: Laser heating; Transparent crystal; VIA Adsorbed atoms; Photon phonon conversion; Master equation; photodesorption.
A coated surface of a crystal is irradiated by intense infrared light. The optically active atomic bonds absorb photons from the laser field, and the subsequent spontaneous decay goes together with emissions of phonons into the crystal. This photon-to-phonon conversion results in an energy flux into the crystal. An equation for this flux is derived from the master equation for the level populations of the dressed atomic states. The saturation limit is discussed, and the general theory is illustrated with two examples. Furthermore, it is outlined with qualitative arguments that the quantum yield of photodesorption is not sensitive to the laser power.