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Measurements of the absolute Raman cross sections of benzene

机译:Measurements of the absolute Raman cross sections of benzene

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The absolute Raman cross sections of the 992 cmminus;1(ring breathing) and 3060 cmminus;1(Cndash;H stretching) modes of benzene are presented at excitation wavelengths of 514.5, 488.0, 441.6, and 325.0 nm. The technique employs a straightforward determination of the total (unrestricted energy bandwidth) scattering cross section along with a simple relative measurement. The effect of the dispersion of the local field correction (via the frequency dependence of the index of refraction) is found to significantly affect the preresonance benzene cross sections and can distort the normally employed lsquo;lsquo;Ahyphen;termrsquo;rsquo; analysis. When the local field effect is incorporated into the data analysis, the results involving neat benzene and previous studies involving 1percnt; benzene in acetonitrile are brought into reasonable agreement. The lsquo;lsquo;n2rsquo;rsquo; solid angle correction is also verified experimentally using air, water, and benzene as test substances. The preresonance enhancement of the 992 cmminus;1mode is found to be consistent with coupling to electronic excitations centered at sim;80 kK which presumably involve the pgr;hyphen;electron system. In contrast, the 3060 cmminus;1mode is coupled to electronic states centered in the deep ultraviolet, at sim;150 kK, which presumably involve the more energetic sgr;hyphen;electron excitations.

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