Abstract
Determination of gap between optically combining states (0-0- transition) from diffuse vibronic absorption or emission spectra is possible now for homogeneous ensembles of chromophores. If the observed spectra present composite polymorphic chromophores or different species they are formed by partial spectra and differing electronic transitions. For these conditions the indicating pure-electronic transition frequency attribute is distorted, smeared or even absent. That behavior is qualitative indication of the chromophore inhomogeneity. The same would be because of impurities. It is shown that the approach of inhomogeneity qualitative indication by spectra is adaptable to different structural forms of chromophor and at polymorphic sites of containing the chromophore media. The experimental data show that the approach is applicable to see the chromophore inhomogeneity by linear and circular vibronic spectra even of molecular dye-labels. The examples of observed distortions for the spectra of different composite species in different media as manifestation of their inhomogeneity are given. As the region of indication 0-0-transition is situated at low intensity antistokes wings of spectra the sensitivity to inhomogeneity is high as to hindrance by impurities and measurement precision.
Highlights
The application of basic quantum-theoretical microscopic reversibility principle to forming spectra mechanism of vibronic transitions with the thermal equilibrium in optical transition starting state have lead to new method of determining gap between combining in vibronic transition electronic states
The method was applied to molecular chromophores in vapor state and solutions [1,2,3], molecular crystals and quantum dots [4], F-centers and doped glasses [5] and molecular markers [4, 6]
Everywhere the homogeneous forms of chromophor gave single definite gap of states combining in electronic transition
Summary
The application of basic quantum-theoretical microscopic reversibility principle to forming spectra mechanism of vibronic transitions with the thermal equilibrium in optical transition starting state have lead to new method of determining gap between combining in vibronic transition electronic states. For all the media the inhomogeneity was observed in different forms of development It was observed evolution of doped glass inhomogeneity with time of annealing up to homogeneous [7] or transformation of diamond nanoparticles with annealing temperature from inhomogeneous form to homogeneous one [8]. It was found that the method is applicable in natural and magnetically induced chirooptics [9] It was shown by this highly selective spectroscopy of complex molecules that integral linear spectra of the chiral substances often show lower homogeneity than chiral spectra.
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