LOCALIZATION OF THE 0–0-TRANSITION IN DIFFUSE VIBRONIC SPECTRA
Abstract
The feasibility of determination of the 0–0-electronic transition ν0 for diffuse absorption, fluorescence and phosphorescence spectra is proposed on the basic principle: direct and reverse transition probabilities between two elemental molecular states are identical. For the starting state being in thermal equilibrium, the transition cross-sections σ obey the relation ( ( ) / )exp( / (2 )) (| |), σ ν ν ν =ϕ ν−ν h kT 0 ϕ is the mirror function about ν0 with «–» and ν>ν0 for absorption, «+» and ν<ν0 for emission respectively. Examples are given of ν0 determined as the extremum of ϕ ν( ) in comparison to the jet-cool spectroscopy data. As a rule, ν0 differs from the maximum of spectra ( ). ν max The width of the area of the extremum of ϕ ν( ) characterizes the inhomogeneity of the spectra.
Keywords
0–0-transition,
diffuse spectra,
electronic transition,
manifestation of tautomerizm,
inhomogeneous broadening
Supporting agencies: The work is sponsored by the Belarusian Republican Foundation for Fundamental Research (Projects Ф16-103 and Ф16К-051).
About the Author
V. A. Tolkachev
B. I. Stepanov Institute of Physics of the National Academy of Sciences of Belarus, Minsk
Russian Federation
Russian Federation
Academician, D. Sc. (Physics and Mathematics), Professor, Chief researcher
68, Nezavisimosti Ave., 220072
References
1. Kazachenko L. P., Stepanov B. I. Mirror symmetry and the contour of luminescence and absorption bands of complex molecules. Optika i Spektroskopiya = Optics and Spectroscopy, 1957, vol. 2, no. 3, pp. 339–349 (in Russian).
2. Dombi I., Kechkemeti I., Kozma L. Contour of spectra of fluorescing solutions. Optika i Spektroskopiya = Optics and Spectroscopy, 1965, vol. 18, pp. 710 (in Russian).
3. Tolkachev V. A. Combining states at electron-vibration transitions of complex molecules and electron transition frequency. Optika i Spektroskopiya = Optics and Spectroscopy, 1966, vol. 20, pp. 982–988 (in Russian).
4. Blokhintsev D. The Spectra of Fluorescence and Absorption of Complex Molecules. Journal Physics, 1939, vol. 1, no. 2, pp. 117–124.
5. Tolkachev V. A. Determination of 0–0 transitions frequency from diffuse electron-vibrational spectra. Journal of Applied Spectroscopy, 2017, vol. 84, no. 4, pp. 668–673. doi.org/10.1007/s10812-017-0527-y
6. Steyer B., Schäfer F. P. Stimulated and Spontaneous Emission from Laser Dyes in the Vapor Phase. Applied Physics, 1975, vol. 7, no. 2, pp. 113–122. doi.org/10.1007/bf00884220
7. Asimov M., Ernsting N. P. Fluorescence excitation spectra of jet-cooled amino-phthalimides. Journal of Luminescence, 1983, vol. 28, no. 1, pp. 119–121. doi.org/10.1016/0022-2313(83)90030-3
8. Borisevich N. A., Gavrilyuk V. V., Povedailo V. A., Tolkachev V. A. Vibration-induced adoption of polarization in fluorescence of free complex molecules. Doklady akademii nauk SSSR = Doklady Physics, 1989, vol. 305, no. 6, pp. 1354–1358 (in Russian).
9. Abakumov G. A., Anisimov Yu. M., Polyakov B. I., Simonov A. P. Spectral, Fluorescent, Photochemical and Laser Properties of Some Organic Compound Vapors. Applied Physics, 1980, vol. 23, no. 1, pp. 83–87. doi.org/10.1007/bf00899574
10. Murakami Jun-ichi, Okuyama K., Ito M. Multiphoton ionization spectrum of p-terphenyl in a supersonic free jet. Bulletin of the Chemical Society of Japan, 1982, vol. 55, no. 11, pp. 3422–3423. doi.org/10.1246/bcsj.55.3422
11. Novak M. J., Szczepaniak K., Barski A., Shugar D. Spectroscopic Studies on Vapor Phase Tautomerism of Natural Bases Found in Nucleic Acids. Zeitschrift fur Naturforschung, 1978, vol. 33, pp. 876–883.
12. Tsuchia J., Tamura T., Fujii M., Ito M. Keto-Enol Tautomer of Uracil and Thymine. The Journal of Physical Chemistry, 1988, vol. 92, no. 7, pp. 1760–1765. doi.org/10.1021/j100318a013
13. Clark L. B., Peschel G. G., Tinoco I. Vapor Spectra and Heats of Vaporization of Some Purine and Pyrimidine Bases. The Journal of Physical Chemistry, 1965, vol. 69, no. 10, pp. 3615–3618. doi.org/10.1021/j100894a063
14. Fujii M., Tamura T., Mikami N., Ito M. Electronic spectra of Uracil in a Supersonic Jet. Chemical Physics Letters, 1986, vol. 126, no. 6, pp. 583–587. doi.org/10.1016/s0009-2614(86)80178-6
15. Brady B. B., Peteanu L. A., Levy D. H. The Electronic Spectra of the Pirimidine Basis Uracil and Thymine in a Supersonic Molecular Beam. Chemical Physics Letters, 1988, vol. 147, no. 6, pp. 538–543. doi.org/10.1016/0009-2614(88)80264-1
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