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International Conference on Laser and Fiber-Optical Networks Modeling

Simulation of intramolecular dynamics at transformation of two light pulses by molecules of active media of photochemical lasers

V. A. Morozov, Dmitry E. Doronkin, Yu. M. Dubina

Published Oct 1, 2008• 0 citations
Publisher

Abstract

Using a numerical solution of a system of equations for matrix elements of file-level model molecule density operator time dependencies of population on its states at different values of two irradiation pulses parameters (the pump pulse and the dump (or probe) pulse) and constants, determining rates of induced radiative transitions of the molecule, and radiative and nonradiative decays of the molecular states are calculated. The values of these constants were taken, in particular, close to these of the corresponding constants of molecules with intramolecular hydrogen bond as the 3-hydroxyflavone (3-HF) molecule. Values of irradiation pulses parameters are obtained, at which after enol-keto photoisomerization, induced by pump pulse, dump pulse induces molecular transition from excited electronic state in keto-form to ground state in this (ldquotautomericrdquo) form. This transition is accompanied by stimulated emission with a frequency of ldquotautomericrdquo fluorescence. Examples of periodic change of intensity of the stimulated emission are given, the frequency of oscillations of fluorescence intensity being proportional to dump pulse intensity.

DOI
10.1109/lfnm.2008.4670374

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Optics and Spectroscopy•May 1, 2012•0 citations
Using a numerical solution of a system of equations for matrix elements of file-level model molecule density operator time dependencies of population on its states at different values of two irradiation pulses parameters (the pump pulse and the dump (or probe) pulse) and constants, determining rates of induced radiative transitions of the molecule, and radiative and nonradiative decays of the molecular states are calculated. The values of these constants were taken, in particular, close to these of the corresponding constants of molecules with intramolecular hydrogen bond as the 3-hydroxyflavone (3-HF) molecule. Values of irradiation pulses parameters are obtained, at which after enol-keto photoisomerization, induced by pump pulse, dump pulse induces molecular transition from excited electronic state in keto-form to ground state in this (ldquotautomericrdquo) form. This transition is accompanied by stimulated emission with a frequency of ldquotautomericrdquo fluorescence. Examples of periodic change of intensity of the stimulated emission are given, the frequency of oscillations of fluorescence intensity being proportional to dump pulse intensity.
The dynamics of transformation of a light pulse by a five-level model molecule whose secondary emission spectrum can contain two fluorescence bands is simulated. The system of equations that determine the time behavior of the matrix elements of the statistical operator of the molecule interacting with the light pulse is numerically solved. From this solution, the time dependences of the populations of the molecular states are determined for different values of the parameters of the irradiation pulse, which is described in terms of the classical theory, and of the parameters that characterize the rates of radiative and nonradiative spontaneous transitions of the molecule. Based on particular examples of the choice of these parameters, it is demonstrated that the mechanism by which dual fluorescence occurs in molecules with intramolecular hydrogen bonds can be efficiently established from the numerically simulated intramolecular dynamics.
A system of equations describing time changes in the matrix elements of the density operator of a seven-level model of a molecule interacting with a light pulse taking into account spontaneous (including collective) decays of molecule excited states is suggested. Model parameters were selected to allow us to perform modeling of the photoisomerization of a molecule with two isomeric states with different stable proton positions on an intramolecular H-bond by numerically solving the suggested system of equations for density operator matrix elements. An analysis of the characteristic time dependences of the population of states of the model under consideration showed that proton phototransfer in the collective decay of various isomeric states of a molecule in an excited electronic state can be one of effective mechanisms of the photoisomerization of molecules whose structure is described by the model.
We model the response of a molecular medium to an intense pulse of light. We begin by reducing the Maxwell-Bloch equations for a multilevel molecular model system to a set of simplified propagation equations. We thereby obtain expressions for the frequency, temperature, and field intensity dependence of the ground and excited electronic state absorption cross sections, and the emission cross section, as well as the temperature dependence of the decay rate of the excited state. The phenomena of saturation, excited-state absorption, optically induced dichroism and birefringence, vibronic energy transfer, induced molecular alignment, decay of the matter-field interaction energy, and rotational diffusion are considered within the general formalism for describing the propagation of an intense pulse of light in the molecular medium. We find that the cross section for absorption (emission) of a photon is not identical to the cross section for molecular excitation (deexcitation) via the matter-field interaction. This is explained in terms of an energy balance between the matter, radiation, the matter-radiation interaction, and the bath responsible for the broadening of the molecular transitions. The inequality of these cross sections determines whether the system supplies or draws energy from the thermal bath. The rise in the vibrational temperature of molecules subjected to an intense short pulse is shown to significantly affect propagation of the pulse. The alignment of the molecular system resulting from saturation of the ground-state transition by a polarized laser pulse and the effects of the orientational dependence of the matter-field interaction including effects of rotational diffusion are determined. As an example of the formalism we consider pulse propagation in a Rhodamine 6G solution. We fit the parameters of the model to determine the frequency dependence of the ground- and excited-state absorption cross sections and the emission cross section and compare with experimentally determined cross sections. We describe the propagation of a pulse whose temporal width is comparable to the rotational diffusion time of the molecules in the dye solution and calculate polarization pulse probe signals.
A mathematical modeling of the time evolution of the populations of the states of a five-level molecule during transformation of resonant monochromatic irradiation and spontaneous emission from the highest-energy state excited by a short pulse of light is performed. The formalism of the optical Bloch equations and quantum theory of radiation are applied a composite system consisting of a molecule and a quantized radiation field. The results of simulation of the evolution of the population of the states of the molecule in the case of spontaneous emission are similar for both of these two approaches, but differ significantly in the case of conversion by the molecule of monochromatic radiation. These differences are the greater, the higher the intensity of resonance Rayleigh scattering or (and) relaxed fluorescence, as a result of which the molecule returns to the initial ground state. An explanation of the nature of these differences is given.
The dynamic quenching of dual fluorescence is simulated based on solving a system of equations for matrix elements of the statistical operator of a five-level model molecule three levels of which belong to its excited states. It is assumed that one of the excited states is resonantly populated by monochromatic irradiation, while the other two states are populated as a result of subsequent relaxation processes. These two states are initial states for transitions that emit dual fluorescence photons. Expressions for the population of the excited molecular states in the case of steady-state fluorescence are obtained taking into account their decay (quenching) due to collisions with foreign molecules of the environment. As applied to molecules with intramolecular hydrogen bonds, the dual fluorescence quenching is described more completely and in more detail compared to the description given in the literature based on the molecular model with two excited levels.
Mathematical modeling of the population dynamics is performed for states of a three-level system (atom) with a V-type configuration transforming a light pulse. It is assumed that the excited eigenstates of the atom are degenerate and coupled by coherent interaction, one of the states being radiating (radiative), while the other state is nonradiating (“dark”). The population dynamics of atomic states is described on the basis of numerical solutions of equations for the matrix elements of the density operator. The dependence of the efficiency of population of the atomic dark state from the values of the parameters of an irradiation pulse and from the ratio of the period of population oscillations of excited atomic states (caused by their coherent interaction) to the lifetime of the atomic radiating state is determined. Typical examples of the time dependence of the population of states of the atom considered are presented for the cases of irradiation by a short (as compared to the lifetime of the radiating state) sinusoidal light pulse and by a long rectangular light pulse with the resonance carrier frequency.