should be observed, as a result of the change in the PES steepness. Curve 2 should
behave similarly. For oscillation appearance, a small velocity of the image points is
necessary, which is ensured by the ‘intersection’ of the PES in the Franck – Condon
zone and the small angle at which they intersect. In this case, the total absorption
cross Sect. 3 is a smooth curve without features.
The presence of this effect accounts for the oscillations of the partial absorption
cross-sections corresponding to the photodecay of CH 3 I into CH 3 + I(
2 P 1/2 ) and
CH 3 + I(
2 P 3/2 ) [81].
References
1. Franck, J., Rabinovitsch, E.: Some remarks about free radicals and the photochemistry of
solutions. Trans. Far. Soc. 30, 120–130 (1934)
2. Pravilov, A.M.: A procedure for the measurements of quantum yields of photoprocesses. High
Energy Chemistry (USSR, Eng. transl.).15, 261-264 (1981)
3. Pravilov, A.M.: Fotoprozessy v molekulyarnykh gasakh (Photoprocesses in molecular gases).
Energoatomizdat, Moscow (1992).(in Russian)
4. Calvert, J.G., Pitts, J.N., Jr.: Photochemistry, J. Willey & Sons, New York, London, Sydney
(1966)
5. Pravilov, A.M.: Radiometry in Modern Scietific Experiments. SpringerWienNew York
(2011). https://doi.org/10.1007/978-3-7091-0104-9
6. Tscherbul, T.V., Buchachenko, A.A., Akopyan, M.E., Poretsky, S.A., Pravilov, A.M.,
Stephenson, T.A.: Collision-induced non-adiabatic transitions between the ion-pair states of
molecular iodine: A challenge for experiment and theory (Invited Article). Phys. Chem.
Chem. Phys. 6, 3201–3214 (2004). https://doi.org/10.1039/b402655a
7. Lukashov, S., Petrov, A., Pravilov, A.: The Iodine Molecule: Insights into Intra- and
Intermolecular Perturbation in Diatomic Molecules. Springer (2018). https://doi.org/10.1007/
978-3-319-70072
8. Noyes, W.A., Leighton, P.A.: The photochemistry of gases. Dover Publication, New York
(1966)
9. Okabe, H.: Photochemistry of small molecules. A Willey Interscience Publication, New York,
Chichester, Brisbane, Toronto (1978)
10. Herzberg, G.: Molecular Spectra and Molecular Structure III. Electronic Spectra and
Electronic Structure of Polyatomic Molecules. Krieger Publishing Company, Second Edition
(1966)
11. Hochstrasser, R.M.: Molecular Aspects of Symmetry. W.A. Benjamin. Inc., New York,
Amsterdam (1966)
12. Braslavsky, S.E.: Glossary of Terms Used in Photochemistry, 3rd edition (IUPAC
Recommendations 2006). Pure Appl. Chem. 79, 293–465 (2007). https://doi.org/10.1351/
pac200779030293
13. Gardner, P.J., Kasha, M.: Electronic consequences of vibrational deficiency in polyatomic
molecules. J. Chem. Phys. 50, 1543–1552 (1968). https://doi.org/10.1063/1.1671240
14. McGlynn, S.P., Azumi, T., Kinoshita, M.: Molecular Spectroscopy of the triplet State.
Prentice-Hall (1969)
15. Mulliken, R.S.: The interpretation of bound spectra. Part IIc. Empirical band types. Rev. Mod.
Phys. 3, 89-155 (1931)
16. Mulliken, R.S.: The halogen moleciles and their spectra. J-J-like coupling. Molecular
ionization potentials. Phys. Rev. 46, 549–571 (1934). https://doi.org/10.1103/PhysRev.46.
549
148
4 Photolysis of Free Molecules
behave similarly. For oscillation appearance, a small velocity of the image points is
necessary, which is ensured by the ‘intersection’ of the PES in the Franck – Condon
zone and the small angle at which they intersect. In this case, the total absorption
cross Sect. 3 is a smooth curve without features.
The presence of this effect accounts for the oscillations of the partial absorption
cross-sections corresponding to the photodecay of CH 3 I into CH 3 + I(
2 P 1/2 ) and
CH 3 + I(
2 P 3/2 ) [81].
References
1. Franck, J., Rabinovitsch, E.: Some remarks about free radicals and the photochemistry of
solutions. Trans. Far. Soc. 30, 120–130 (1934)
2. Pravilov, A.M.: A procedure for the measurements of quantum yields of photoprocesses. High
Energy Chemistry (USSR, Eng. transl.).15, 261-264 (1981)
3. Pravilov, A.M.: Fotoprozessy v molekulyarnykh gasakh (Photoprocesses in molecular gases).
Energoatomizdat, Moscow (1992).(in Russian)
4. Calvert, J.G., Pitts, J.N., Jr.: Photochemistry, J. Willey & Sons, New York, London, Sydney
(1966)
5. Pravilov, A.M.: Radiometry in Modern Scietific Experiments. SpringerWienNew York
(2011). https://doi.org/10.1007/978-3-7091-0104-9
6. Tscherbul, T.V., Buchachenko, A.A., Akopyan, M.E., Poretsky, S.A., Pravilov, A.M.,
Stephenson, T.A.: Collision-induced non-adiabatic transitions between the ion-pair states of
molecular iodine: A challenge for experiment and theory (Invited Article). Phys. Chem.
Chem. Phys. 6, 3201–3214 (2004). https://doi.org/10.1039/b402655a
7. Lukashov, S., Petrov, A., Pravilov, A.: The Iodine Molecule: Insights into Intra- and
Intermolecular Perturbation in Diatomic Molecules. Springer (2018). https://doi.org/10.1007/
978-3-319-70072
8. Noyes, W.A., Leighton, P.A.: The photochemistry of gases. Dover Publication, New York
(1966)
9. Okabe, H.: Photochemistry of small molecules. A Willey Interscience Publication, New York,
Chichester, Brisbane, Toronto (1978)
10. Herzberg, G.: Molecular Spectra and Molecular Structure III. Electronic Spectra and
Electronic Structure of Polyatomic Molecules. Krieger Publishing Company, Second Edition
(1966)
11. Hochstrasser, R.M.: Molecular Aspects of Symmetry. W.A. Benjamin. Inc., New York,
Amsterdam (1966)
12. Braslavsky, S.E.: Glossary of Terms Used in Photochemistry, 3rd edition (IUPAC
Recommendations 2006). Pure Appl. Chem. 79, 293–465 (2007). https://doi.org/10.1351/
pac200779030293
13. Gardner, P.J., Kasha, M.: Electronic consequences of vibrational deficiency in polyatomic
molecules. J. Chem. Phys. 50, 1543–1552 (1968). https://doi.org/10.1063/1.1671240
14. McGlynn, S.P., Azumi, T., Kinoshita, M.: Molecular Spectroscopy of the triplet State.
Prentice-Hall (1969)
15. Mulliken, R.S.: The interpretation of bound spectra. Part IIc. Empirical band types. Rev. Mod.
Phys. 3, 89-155 (1931)
16. Mulliken, R.S.: The halogen moleciles and their spectra. J-J-like coupling. Molecular
ionization potentials. Phys. Rev. 46, 549–571 (1934). https://doi.org/10.1103/PhysRev.46.
549
148
4 Photolysis of Free Molecules