Quantum yields and potential energy surfaces: A theoretical study

Journal of Physical Organic Chemistry

Volumn 20, Issue 11, 2007, Pages 821-829

  Nakamura, Shinichiro ^a   Kobayashi, Takao ^a   Takata, Atsushi ^b   Uchida, Kingo ^b   Asano, Yukako ^a   Murakami, Akinori ^a   Goldberg, Alexander ^a   Guillaumont, Dominique ^a   Yokojima, Satoshi ^a   Kobatake, Seiya ^c   Irie, Masahiro ^d  

^a MITSUBISHI CHEMICAL CORPORATION   (Japan)

^b RYUKOKU UNIVERSITY   (Japan)

^c Osaka Prefecture University   (Japan)

^d KYUSHU UNIVERSITY   (Japan)

Author keywords

Photochromism; Potential energy surface; Quantum yield; Theoretical study

Indexed keywords

EXCITED STATES; GROUND STATE; PHOTOCHROMISM; POTENTIAL ENERGY SURFACES; THERMODYNAMIC STABILITY;

CONICAL INTERSECTIONS; CYCLOREVERSION REACTIONS; ENERGY MINIMA; PHOTOCHROMIC CYCLIZATION; THEORETICAL STUDY;

QUANTUM YIELD;

EID: 36349027070     PISSN: 08943230     EISSN: 10991395     Source Type: Journal    
DOI: 10.1002/poc.1245     Document Type: Conference Paper

References (31)

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5. (d) See Chapter II of the Reference 2c for the discussion of the ab-initio method for excited states. The detailed information on the quality of the wave functions (CASSCF, CASPT2), dynamic correlation and basis sets are presented by Merchan, M and Serrano-Andres, L;
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17. (a) Uchida K, Guillaumont D, Tsuchida E, Mochizuki G, Irie M, Murakami A, Nakamura S. J Mol. Struct. (Theochem) 2002; 579: 115-120;
18. (b) To predict the relative positions of the relatively ionic character IB state and the neutral character 2A state in energy is difficult. The detailed discussions are reported for general polyene molecules, for example, Nakatsuji H, Kitao O, Komori M. In Lecture Notes in Chemistry, 50, Mukherjee D (ed.), pp. 101-122, Springer-Verlag: Berlin Heidelberg 1989, and references cited therein.
19. Uchida K, Tsuchida E, Aoi Y, Nakamura S, Irie M. Chem. Lett. 1999; 28: 63-64.
20. Kobatake S, Irie M. Bull. Chem. Soc. Jpn. 2004; 77: 195-210.
21. Asano Y, Murakami A, Kobayahsi T, Kobatake S, Irie M, Yabushita S, Nakamura S. J Mol. Struct. (Theochem) 2003; 625: 227-234.
22. Nakamura S, Kanda K, Guillaumont D, Uchida K, Irie M. Nonlinear Opt. 2000; 26: 201-205.
23. (a) Guillaumont D, Kobayashi T, Kanda K, Miyasaka H, Uchida K, Kobatake S, Shibata K, Nakamura S, Irie M. J. Phys. Chem. A. 2002; 106: 7222-7227;
24. (b) Asano Y, Murakami A, Kobayahsi T, Goldberg A, Guillaumont D, Yabushita S, Irie M, Nakamura S. J. Am. Chem. Soc. 2004; 126: 12112-12120.
25. (a) The results obtained by the CASSCF level of the calculations are shown in Figure 3. However, for the accurate relative position of IB and 2A, dynamic correlations are to be considered as was discussed in reference 14b. Nonetheless, it is likely that the shift from the photochemically allowed 1B state to the dark 2A state will occur in the cycloreversion reaction, and the QY factor will be determined by the energy profile of the 2A PES on the basis of the fact that the experimental QY reflects the valueΔE as discussed in 3.3; (b) The relative position of CI such as the energy level of 2A/1A CI(O) from 2Ao will be sensitive to the substituents that are truncated in the frame molecule shown in Figure 3. See the Reference 14b for the detailed discussion.
26. Morimitsu K, Kobatake S, Nakamura S, Irie M. Chem. Lett. 2003; 32: 858-859.
27. In the correlation shown in Figure 4, there are at least two approximations. The first one is that the valueΔE is used instead of the transition state energy. The second one is that the locations of CI for each molecule are not determined; the CIs have been obtained only for the frame model molecule (N), in which the energy gap of 2A/1A CI (O) from the 2Ao minimum is large. As was discussed in reference 14b, the position of the CI can also be the critical factor. These are important subjects of the future study as well as the dynamics of the trajectories.
28. Uchida K, Irie M. Chem. Lett. 1995; 24: 969-970.
29. A theoretical study on (I)-type cyclization focusing on the rotational isomerization and QY in various molecules is reported. Experimental NMR chemical shifts as a function of temperature are used to monitor the isomerization; Goldberg A, Murakami A, Kanda K, Kobayashi T, Nakamura S, Uchida K, Sekiya H, Fukaminato T, Kawai T, Kobatake S, Irie M. J. Phys. Chem. A. 2003; 107: 4982-4988.
30. Electrochemical approaches can be an aid for additional experimental information. The theoretical and experimental joint studies on cycloreversion reactions by electrochemical methods are reported: (a) Matsuda K, Yokojima S, Moriyama Y, Nakamura S, Irie M. Chem. Lett. 2006; 35: 900-901;
31. (b) Yokojima S, Matsuda K, Irie M, Murakami A, Kobayashi T, Nakamura S. J. Phys. Chem. A. 2006; 110: 8137-8143.