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At least 991 records · Page 55

Theory of Intramolecular Relaxation Processes

A master equation is derived to describe internal relaxation processes in molecular systems with a relatively small number of degrees of freedom. It is an inhomogeneous equation, taking into account nondiagonal elements of the coarse‐grained density matrix which prove to be the most relevant ones for the problem under consideration. Various relaxational time scales, inherent in a molecular system, can thus be shown to exist. Relaxation mechanisms and equilibrium states on these time scales can be determined. The general character and different types of solutions of the master equation are investigated. The theory is applied to internal vibrational relaxation and intramolecular rearrangement (isomerization) reactions.

Hofacker, G. Ludwig↗

Theory of a high-intensity gas laser

Single mode gas laser theory for arbitrary field intensities in terms of ensemble averaged form of density-matrix equations of motion

Feld, M. S.↗

Resonance spectra of a paramagnetic probe dissolved in a viscous medium

A model is presented for calculating the paramagnetic resonance (EPR) spectrum of vanadyl acetylacetonate (VAAC) dissolved in either a liquid crystal or isotropic solvent. It employs density matrix formulation in the rotating reference frame. The molecules occupy several discrete angles with respect to the magnetic field and can relax to neighboring positions in a characteristic time tau(theta). The form of tau(theta) is found from a diffusion approach, and the magnitude of tau(theta) is a measure of how freely the VAAC probe tumbles in the solvent. Spectra are predicted for values of tau between 10 to the minus 11th power sec and 10 to the minus 7th power sec. The EPR spectrum, in the isotropic case, is obtained be summing the contributions from the allowed angles weighted by the polar volume element, sin theta. When applying the model to the nematic liquid crystal case it is also necessary to multiply by the Saupe distribution function. For this case tau(theta) is obtained from the diffusion approach in which two diffusion constants are employed to reflect the difference in the parallel and perpendicular components of the viscosity.

Kaplan, J. I.↗

Basic characteristics of high-frequency Stark-effect modulation of CO2 lasers.

The molecular Stark effect and its application to the modulation of infrared laser radiation have been investigated both theoretically and experimentally. Using a density matrix approach, a quantum mechanical description of the effect of a time-varying electric field on the absorption coefficient and refractive index of a molecular gas near an absorption line has been formulated. For modulation applications a quantity known as the ?modulation depth' is of prime importance. Theoretical expressions for the frequency dependence of the modulation depth show that the response to the frequency of a time-varying Stark field is separated into a nondispersive and a dispersive region, depending on whether the modulating frequency is less than or greater than the homogeneous absorption linewidth. Experimental results showing nondispersive modulation at frequencies to 30 MHz are presented. In addition it is shown that the response of modulation depth to Stark field amplitude is separated into linear and nonlinear regions, the field at which nonlinearities begin being determined by the absorption spectrum of the molecule being used.

Claspy, P. C.↗

Quantum-mechanical transport equation for atomic systems.

A quantum-mechanical transport equation (QMTE) is derived which should be applicable to a wide range of problems involving the interaction of radiation with atoms or molecules which are also subject to collisions with perturber atoms. The equation follows the time evolution of the macroscopic atomic density matrix elements of atoms located at classical position R and moving with classical velocity v. It is quantum mechanical in the sense that all collision kernels or rates which appear have been obtained from a quantum-mechanical theory and, as such, properly take into account the energy-level variations and velocity changes of the active (emitting or absorbing) atom produced in collisions with perturber atoms. The present formulation is better suited to problems involving high-intensity external fields, such as those encountered in laser physics.

Berman, P. R.↗

Resonance spectra of a paramagnetic probe dissolved in a viscous medium.

The paramagnetic resonance spectrum of Vanadyl acetylacetonate (VAAC) dissolved in either a liquid crystal or isotropic solvent is calculated with the aid of a presented model. Density matrix formulation is employed in the rotating reference frame. The molecules occupy several discrete angles with respect to the magnetic field and can relax to neighboring positions in a characteristic time. The form of this characteristic time is found from a diffusion approach, and the magnitude of this time is a measure of how freely the VAAC probe tumbles in the solvent. Spectra are predicted for time values ranging from 10 picoseconds to 10 microseconds.

Kaplan, J. I.↗

Polarization phenomena in multiphoton ionization of atoms

The theory of multiphoton ionization for an atomic system of arbitrary complexity is developed using a density matrix formalism. An expression is obtained which determines the differential N-photon ionization cross section as a function of the polarization states of the target atom and the incident radiation. The parameters which characterize the photoelectron angular distribution are related to the general reduced matrix elements for the N-photon transition. Two-photon ionization of unpolarized atoms is treated as an illustration of the use of the theory. The dependence of the multiphoton ionization cross section on the polarization state of the incident radiation, which has been observed in two- and three-photon ionization of Cs, is accounted for by the theory. Finally, the photoelectron spin polarization produced by the multiphoton ionization of unpolarized atoms, like the analogous polarization resulting from single-photon ionization, is found to depend on the circular polarization of the incident radiation.

Jacobs, V. L.↗

Redistribution of resonance radiation. II - The effect of magnetic fields.

Previously obtained results for scattering of radiation in the presence of collisions are restated in a density matrix formalism which employs an irreducible-tensor description of the radiation field. This formalism is particularly useful for problems associated with radiative transfer theory. The redistribution is then extended to include the effect of a weak magnetic field. By averaging over a finite bandwidth which is on the order of the Doppler width, simplified expressions of physical significance for the scattering in the Doppler core and the Lorentz wings are obtained. Expressions are also obtained for the corresponding source function of radiative transfer theory.

Omont, A.↗

Polarization phenomena in multiphoton ionization of atoms.

The theory of multiphoton ionization for an atomic system of arbitrary complexity is developed using a density matrix formalism. An expression is obtained which determines the differential N-photon ionization cross section as a function of the polarization states of the target atom and the incident radiation. The parameters which characterize the photo-electron angular distribution are related to the general reduced matrix elements for the N-photon transition. Two-photon ionization of unpolarized atoms is treated as an illustration of the use of the theory. The dependence of the multiphoton ionization cross section on the polarization state of the incident radiation, which has been observed in two- and three-photon ionization of Cs, is accounted for by the theory. Finally, the photoelectron spin polarization produced by the multiphoton ionization of unpolarized atoms, like the analogous polarization resulting from single-photon ionization, is found to depend on the circular polarization of the incident radiation.

Jacobs, V. L.↗

System for automated measurement of full-scale noises and vibrations

On-line devices are described for measuring the electrical spectrum of a signal in the presence of full scale noise and vibrations. The system includes a set of parallel filters with detectors at the filtration channel outlet. A reciprocal spectral density matrix is used to process the information contained in the interacting signals from various noise and vibration sources.

Lyubashevskiy, G. S.↗

The spin-temperature theory of dynamic nuclear polarization and nuclear spin-lattice relaxation

A detailed derivation of the equations governing dynamic nuclear polarization (DNP) and nuclear spin lattice relaxation by use of the spin temperature theory has been carried to second order in a perturbation expansion of the density matrix. Nuclear spin diffusion in the rapid diffusion limit and the effects of the coupling of the electron dipole-dipole reservoir (EDDR) with the nuclear spins are incorporated. The complete expression for the dynamic nuclear polarization has been derived and then examined in detail for the limit of well resolved solid effect transitions. Exactly at the solid effect transition peaks, the conventional solid-effect DNP results are obtained, but with EDDR effects on the nuclear relaxation and DNP leakage factor included. Explicit EDDR contributions to DNP are discussed, and a new DNP effect is predicted.

Byvik, C. E.↗

Diagrammatic evaluation of the density operator for nonlinear optical calculations

Time-ordered diagrammatic representations are shown to precisely define and to simplify calculations of radiative perturbations to the density matrix. Nonlinear optical susceptibilities, here exemplified by that of CARS, can be obtained by simple propagator rules. An interpretation of transient Raman scattering in terms of time-ordered contributions is also discussed.

Yee, S. Y.↗

Laser amplification of incoherent radiation

The amplification of noise in a laser amplifier is treated theoretically. The model for the active medium and its description using density-matrix techniques, are taken from the theory of laser operation. The spectral behavior of the radiation in the nonlinear regime is studied and the formalism is written from the onset in the frequency domain. The statistics of the light are gradually modified by the nonlinear amplification process, and expressions are derived for the rate of change of fluctuations in intensity as a measure of statistical changes. In addition, the range of validity of Litvak's Gaussian-statistics approximation is discussed. In the homogeneous-broadening case, the evolution of initially broadband Gaussian radiation toward quasimonochromatic oscillations with laserlike statistics is explored in several numerical examples. The connections of this study with the time-domain work on self-pulsing in a ring-laser configuration, are established. Finally, spectral-narrowing and -rebroadening effects in Doppler-broadened media are discussed both analytically and with numerical examples. These examples show the distinct contribution of pulsations in the population ('Raman-type terms'), and saturation phenomena.

Menegozzi, L. N.↗

Diagrammatic analysis of the density operator for nonlinear optical calculations Pulsed and CW responses

In the present paper a diagrammatic analysis of the density operator for the evaluation of nonlinear optical quantities is considered. The present approach extends earlier diagrammatic analysis by treating the time evolution of both the wave function and its complex conjugate. Time-ordered graphs result, each of which corresponds to a term in the density matrix. Examples involving the third-order susceptibility are discussed for both monochromatic and pulse excitation. In particular coherent rotational transient birefringence is discussed. The diagrams provide a convenient means by which nonlinear optical processes can be precisely defined and the susceptibility readily evaluated.

Yee, T. K.↗

On redistribution and the equations for radiative transfer

The derivation of the equations of statistical equilibrium are outlined, starting from the quantum density-matrix equations, drawing particular attention to the approximations and assumptions used in the development of tractable expressions. Then, using the quantum-fluctuation-regression theorem, emission and absorption coefficients are obtained for multilevel atomic systems which are nondegenerate except for m-substates. These coefficients are valid to first order in the incident intensity. Possible extensions to higher intensity broadband incoherent fields are suggested.

Cooper, J.↗