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See Computational Details for a general discussion of self- interaction error (SIE) in current DFT implementations. All spin distributions were recomputed with various hybrid and gradient-corrected density functionals, such as MPW1K, B3PW1K, MPW1PW91 and BP86. Very good internal consistency of all computed spin densities had been found with no discrepancy between the recomputed spin densities and our presented B3LYP data, conclusively showing that the SIE has no bearing on the results we report in our study.
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See Computational Details for a general discussion of self- interaction error (SIE) in current DFT implementations. All spin distributions were recomputed with various hybrid and gradient-corrected density functionals, such as MPW1K, B3PW1K, MPW1PW91 and BP86. Very good internal consistency of all computed spin densities had been found with no discrepancy between the recomputed spin densities and our presented B3LYP data, conclusively showing that the SIE has no bearing on the results we report in our study.
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The assignment of the spin state of the ruthenium center on the basis of a Mulliken spin population analysis is the most commonly used procedure despite its well-known limitations. The well-known problem is that calculated Mulliken spin values come out somewhat lower than the ideal spins, i.e, 1.0 for an electronic doublet spin state. However, relative Mulliken spin values are more reliable and informative than absolute values. Therefore, we compare Mulliken populations for different dye complexes in order to reliably determine the change in oxidation state of the ruthenium center. The localization of the spin density is illustrated via spin density maps, and it has been verified by orbital population analyses
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The assignment of the spin state of the ruthenium center on the basis of a Mulliken spin population analysis is the most commonly used procedure despite its well-known limitations. The well-known problem is that calculated Mulliken spin values come out somewhat lower than the ideal spins, i.e., 1.0 for an electronic doublet spin state. However, relative Mulliken spin values are more reliable and informative than absolute values. Therefore, we compare Mulliken populations for different dye complexes in order to reliably determine the change in oxidation state of the ruthenium center. The localization of the spin density is illustrated via spin density maps, and it has been verified by orbital population analyses.
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