| Autor: |
Vöhringer, P., Arnett, D. C., Westervelt, R. A., Feldstein, M. J., Scherer, N. F. |
| Předmět: |
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| Zdroj: |
Journal of Chemical Physics; 3/8/1995, Vol. 102 Issue 10, p4027, 10p |
| Abstrakt: |
The connection between dephasing of optical coherence and the measured spectral density of the pure solvent is made through measurements and calculations of photon echo signals. 2-pulse photon echo measurements of a cyanine dye in polar solvents are presented. Signals are recorded for both phase matched directions enabling accurate determination of the echo signal time shift. Echo signals are calculated by two approaches that employ the response function description of nonlinear spectroscopy; (i) a single Brownian oscillator line shape model, and (ii) the line shape obtained using the solvent spectral density. The strongly overdamped Brownian oscillator model incorporates only a single adjustable parameter while the experimental data present two fitting constraints. The second model incorporates the measured solvent spectral density. Both give very good agreement with the experimental results. The significance of the second method lies in this being a new approach to calculate nonlinear spectroscopic signals, for comparison with experimental data, that uses directly the measured spectrum of equilibrium fluctuations of the solvent. This approach also provides a better conceptual perspective for deriving insight into the nature of the solute–solvent coupling mechanism. Comparing the parameters for the strength of interaction in a variety of polar solvents it is found that the coupling involves the solvent polarizability and not the solvent polarity. The interaction mechanism cannot be deduced from the Brownian oscillator calculations. © 1995 American Institute of Physics. [ABSTRACT FROM AUTHOR] |
| Databáze: |
Complementary Index |
| Externí odkaz: |
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