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The Journal of Physical Chemistry

Effects of Solute Electronic Structure Variation on Photon Echo Spectroscopy

Badry D. Bursulaya, Hyung J. Kim

Published Jan 1, 1996• 21 citations
Publisher

Abstract

Two-pulse photon echo spectroscopy for dipolar solutes in water is studied via equilibrium and nonequilibrium molecular dynamics (MD) simulations. By extension of the valence-bond description employed in our earlier MD work [Bursulaya, B. D.; Zichi, D. A.; Kim, H. J. J. Phys. Chem. 1995, 99, 10069; 1996, 100, 1392], both the solute ground- and excited-state electronic polarizabilities are incorporated into the simulations. By modulation of the static transition frequency distribution and solvation dynamics, the state-dependent solute electronic structure variation is found to have a significant influence on the echo; its relaxation behavior with pulse delay is slower for a polarizable solute than for a nonpolarizable one. Despite their similar overall effects, however, the ground- and excited-state polarizabilities modulate the echo via rather different mechanisms. Equilibrium and nonequilibrium MD yields similar results for a nonpolarizable solute but discernible differences for a polarizable solute.

DOI
10.1021/jp961001+

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Two-pulse photon echo spectroscopy for dipolar solutes in water is studied via equilibrium and nonequilibrium molecular dynamics (MD) simulations. By extension of the valence-bond description employed in our earlier MD work [Bursulaya, B. D.; Zichi, D. A.; Kim, H. J. J. Phys. Chem. 1995, 99, 10069; 1996, 100, 1392], both the solute ground- and excited-state electronic polarizabilities are incorporated into the simulations. By modulation of the static transition frequency distribution and solvation dynamics, the state-dependent solute electronic structure variation is found to have a significant influence on the echo; its relaxation behavior with pulse delay is slower for a polarizable solute than for a nonpolarizable one. Despite their similar overall effects, however, the ground- and excited-state polarizabilities modulate the echo via rather different mechanisms. Equilibrium and nonequilibrium MD yields similar results for a nonpolarizable solute but discernible differences for a polarizable solute.
The decay of three-pulse photon echo signals from a solute in a liquid solvent is sensitive to the solute’s transition frequency fluctuations, as characterized by its two-point time correlation function, otherwise known as the solvation correlation function. The most widely used method for determining this solvation correlation function from photon echo data involves the three-pulse photon echo peak shift (3PEPS) method. Using this method the long-time decay of the solvation correlation function can be obtained directly, but the determination of the short-time decay requires a difficult numerical fitting procedure. In this study we propose several alternative approaches to determining the solvation correlation function from echo data, the most promising and straightforward of which we call the S3PE (short-time slope of the three-pulse photon echo) method. The accuracy and efficacy of this approach is illustrated by extracting the solvation correlation function from “experimental” data obtained from classical molecular dynamics computer simulations.
We calculate the signal in a time-resolved, coherent light scattering experiment on a dilute solution of a nonpolar solute dissolved in a nonpolar solvent. We model the solute and solvent molecules as electronic two level systems, and assume that only the solute interacts with radiation. The electronic degree of freedom is treated perturbatively within the Born–Oppenheimer approximation. The nuclear degrees of freedom are treated classically, and their effects are modeled by a molecular dynamics simulation. We assume the electronic absorption spectrum is dominated by inhomogeneous broadening. The validity of this assumption for our model is verified through the calculation of the absorption line shape with and without the inhomogeneous broadening assumption. A quantitative measure of the homogeneous dephasing time is obtained from a calculation of the photon echo signal for our model. The time dependence of the light scattering signal is shown to reflect both dynamics of the fluid in its electronic ground state and in its electronic excited state. We analyze the relative importance of contributions to the signal from these two types of dynamics as a function of experimental time scale and laser frequency.
A rigorous theoretical connection between the polarizability spectral density obtained from optical Kerr effect (OKE) measurement with the correlation function describing solvent-induced optical dephasing detected in photon echo measurements is given. The experimentally obtained spectral density has a more reasonable physical basis than model correlation function descriptions of solvent fluctuations. The experimental OKE spectrum is demonstrated to provide a natural description of solvent motions that modulate the chromophore electronic states in the case of weak induced-dipolar interactions. The chromophore optically active vibrational modes are obtained from pump-probe spectra and are employed in the calculation of echo signals. It is found that the fast decays of the two-pulse echo signals result from both solvent and solute intramolecular motions while the echo peak shifts are dominated by the solvent intermolecular modes.
The nonperturbative approach to the calculation of nonlinear optical spectra of Seidner et al. [J. Chem. Phys. 103, 3998 (1995)] is extended to describe four-wave mixing experiments. The system-field interaction is treated nonperturbatively in the semiclassical dipole approximation, enabling a calculation of third order nonlinear spectroscopic signals directly from molecular dynamics and an efficient modeling of multilevel systems exhibiting relaxation and transfer phenomena. The method, coupled with the treatment of dynamics within the Bloch model, is illustrated by calculations of the two-dimensional three-pulse photon echo spectra of a simple model system-a two-electronic-level molecule. The nonperturbative calculations reproduce well-known results obtained by perturbative methods. Technical limitations of the nonperturbative approach in dealing with a dynamic inhomogeneity are discussed, and possible solutions are suggested. An application of the approach to an excitonically coupled dimer system with emphasis on the manifestation of complex exciton dynamics in two-dimensional optical spectra is presented in paper II Pisliakov et al. [J. Chem. Phys. 124, 234505 (2006), following paper].
Abstract This account summarizes our recent work on measurements of the correlation function of the transition frequency fluctuations by a three-pulse photon echo method. The correlation function of the transition frequency fluctuations is a sensitive measure for the magnitudes and time scales of dynamical interactions between solute and solvent. We describe the results of the solvation dynamics of small ions in protic solvents such as methanol and water obtained by an infrared photon echo method.
The semiconductor Bloch equations are solved numerically for a two-pulse photon-echo configuration. The time-dependent diffracted signal is computed and the significance of many-body effects, carrier relaxation, and dephasing is investigated in detail. Assuming femtosecond-pulse excitation at various intensities and frequencies, distinctly different results are obtained if the exciton or the continuum electron-hole-pair states are excited. It is shown that pure exciton excitation produces a free-induction decay signal and no photon echo. An echo signal is obtained only if continuum states are excited either directly by choosing the central pulse frequencies appropriately or if the band-gap renormalization is sufficiently strong to shift continuum states into resonance. A continuous transition between free-induction decay and photon-echo signal is obtained with increasing excitation amplitude. A perturbative analytical analysis of the equations allows one to identify the role of the many-body effects in producing the different features.