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Energies and energy gaps oscillate during the geometry optimization and never converge, or if energy gap tends to converge the energy increases endlessly. This behavior has been found to be associated with highly sloped conical intersections.
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Since the irradiation wavelength can be changed without removing the sample from the FTIR spectrometer, the concentrations in photoequilibrium for different irradiation wavelengths can be determined with high accuracy (and independent of any spectrometer drifts) relative to the value at 255 nm by comparing the peak-to-peak differences in the FTIR-difference spectra shown in Figure 1d).
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33
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3242741015
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Note, however, that the sample can be efficiently destroyed upon irradiation with an unfiltered low-pressure Hg lamp, which we attribute to excitation by light from the 193-nm line.
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T is the ratio of initially excited cis and trans molecules.
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-1 region, which can be easily subtracted as a linear background from the transient data. It stays constant at delay times longer than 100 ps, indicating the end of the main energy dissipation.
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41
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3242717702
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note
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0 CASPT2 energy values reported in Table 5S in Supporting Information. Energy degeneracy was achieved at the CASSCF level of theory, but the CASPT2 treatment split the two energies. The mean values represent a good approximation of the energy of the CI.
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