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See the Supporting Information for calculation details
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See the Supporting Information for calculation details.
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41
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0034728567
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One referee suggested that it is better to explain the shape of the Frank-Condon (FC) region to see in which direction the reaction can take place. The FC point is not a real first-order saddle point. The reason for this is simply because its energy gradient does not go to zero. Even if we draw the picture about the potential-energy surface around the FC point, it is still difficult to recognize in which direction the reaction can take place. Nevertheless, in our study we use figures to represent, for example, the barrier heights, from which one may at least have a quantitative picture about the photochemical reactions. For details, one may see: A. Sanchez-Galvez, P. Hunt, M. A. Robb, M. Olivucci, T. Vreven, H. B. Schlegel, J. Am. Chem. Soc. 2000, 122, 2911.
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One referee suggested that it is better to explain the shape of the Frank-Condon (FC) region to see in which direction the reaction can take place. The FC point is not a real first-order saddle point. The reason for this is simply because its energy gradient does not go to zero. Even if we draw the picture about the potential-energy surface around the FC point, it is still difficult to recognize in which direction the reaction can take place. Nevertheless, in our study we use figures to represent, for example, the barrier heights, from which one may at least have a quantitative picture about the photochemical reactions. For details, one may see: A. Sanchez-Galvez, P. Hunt, M. A. Robb, M. Olivucci, T. Vreven, H. B. Schlegel, J. Am. Chem. Soc. 2000, 122, 2911.
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37449028341
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The IRC results have highlighted the usefulness of this technique in elucidating reaction mechanisms and have clearly demonstrated what kind of reactions are involved. Those reactions that we have investigated (i.e, paths A-1, A-2, C-1, C-2, C-3, D-1, D-2, D-3, F-1, F-2, F-3, G, H) have been probed in some detail by determining the IRC[17a] with the algorithm proposed by Schlegel[17b
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[17b].
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However, it was also reported that at least five minor photoproducts (total 13%) were observed but were not isolated in sufficient quantities for complete characterization. For details, see reference [8].
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However, it was also reported that at least five minor photoproducts (total 13%) were observed but were not isolated in sufficient quantities for complete characterization. For details, see reference [8].
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