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2442759688
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2442727720
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note
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333, and the light is z-polarized, the variance induced in the x direction due to orientational fluctuations is described as follows (where N is the number of chromophores and v is the volume): (Formula Presented)
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25
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2442746919
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s is essentially constant in the low solute concentration range studied
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s is essentially constant in the low solute concentration range studied.
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26
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0030149143
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(b) ref 16
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2442754288
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note
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The assignment of the 430 nm band as an IL transition is supported by an acid addition experiment. Protonating the ammine nitrogens causes the band to shift to ca. 320 nm while leaving the 510 nm band relatively unperturbed. If the 430 nm band had been MLCT in nature, protonation would have created a better electron acceptor and caused the band to red shift.
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33
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36849097205
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2442747648
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note
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The indices on the hyperpolarizability tensor are used to denote coordinates. Numbers are used to describe the relevant tensor components within the molecular framework, and letters are used to describe the components observed within the laboratory frame of reference. A more complete discussion can be found in ref 33.
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36
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0031073050
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37
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2442746184
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note
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333. The maximum polarization ratio expected is still 1.5.
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38
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0000936492
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2442755150
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The internal field was assumed to be 1.3 times the externally applied field
-
The internal field was assumed to be 1.3 times the externally applied field.
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40
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0030134513
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For a cautionary discussion of deconvolution and "uniqueness of fit" problems in electroabsorption spectroscopy, see: Bublitz, G. U.; Laidlaw, W. M.; Denning, R. G.; Boxer, S. G. J. Am. Chem. Soc. 1998, 720, 6068. In principle, the "uniqueness" problem can be at least partially resolved by utilizing higher order Stark spectroscopy. Unfortunately, we were unable to obtain higher order signals.
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44
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0001393783
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Alternate two-level descriptions are also available, which would increase the values of β calculated here by as much as a constant factor of 4. A full discourse on conventions for NLO can be found in the following: Willens, A.; Rice, J. E.; Burland, D. M.; Shelton, D. P. J. Chem. Phys. 1992, 97, 7590.
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2442749894
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note
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2, the expected total contribution would be the same for either assignment.
-
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47
-
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2442738826
-
-
note
-
It is also probable that the changes in dipole moment are not in direct opposition to each other. The transition moments for the IL and MLCT transitions are almost certainly offset by some finite angle (see Scheme 1).
-
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48
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0030913631
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