Aspects of intervalence charge transfer in cyanide-bridged systems: Modulated electric field assessment of distances, polarizability changes, and anticipated first hyperpolarizability characteristics

Journal of Physical Chemistry A

Volumn 102, Issue 43, 1998, Pages 8320-8324

  Vance, Fredrick W ^a   Karki, Laba ^a   Reigle, James K ^a   Hupp, Joseph T ^a   Ratner, Mark A ^a  

^a NORTHWESTERN UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0038085864     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp981352j     Document Type: Article

References (41)

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22. 2b
23. 12 values in compounds 3 and 6 could be as large as 23°. Thus, when viewed as contributions along the charge-transfer axis, the overall variance could be even smaller than reported here.
24. 12 values are 3.8 and 3.5 Å, respectively (versus 3.5 Å in the present study).
25. It should be noted that the "donor orbital specific" values previously reported for compound 3 are dependent on the deconvolution methodology employed for both the absorption and electroabsorption spectra. Boxer and co-workers have pointed out (ref 10 and Bublitz, G. U.; Boxer, S. G., private communication) that even for spectra acquired at 77 K, attempted deconvolutions may not be unique. Indeed, they find that satisfactory fits for 3 can be acheived by assigning identical electrooptical parameters to the overlapping transitions. A further indication that deconvolution problems exist is observation of a (presumably artifactual) dependence of the deconvolution outcomes on temperature (77 and 298 K.; Karki and Vance, unpublished data). Thus, in this work, we have reported results from a fit of the total line shape for compounds 3 and 6. We are optimistic that planned absorption and electroabsorption experiments at near liquid He temperatures will provide spectra that are sufficiently resolved to permit unique deconvolutions.
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