Solvents effects on spectra

For a more detailed discussion of state designations and orbital promotions, see the papers of Platt (1953), Matsen (1956), Robinson (1961), Kasha (1961). Criteria for distinguishing between n — p and transitions are summarized in Sidman s (1958) review. It may be mentioned that an analysis of solvent effects on spectra is one of the most generally employed tools for preliminary diagnosis of the character of an electronic transition, a point which will be discussed further in connection with model studies for difference spectra of proteins (Section VI,X)). 

Ya. L. Gol dfarb. Izvest. Akad. Nauk S.S.S.R., Otdel. Khim. Nauk 1956, 12Q-6. IR solvent effect on spectra of 2-aminopyridine, 2-pyri-donimine. 

Japan 60, 595-603 (1939). UV chelation and solvent effect on spectra, 0-, o -dihy-droxyazo compounds and their salts. 

UV spectra of pyridazines and pyridazinones were recorded, and solvent effects on spectra were examined. jjjg absorption spectrum of the... 

An intramolecular charge transfer toward C-5 has been proposed (77) to rationalize the ultraviolet spectra observed for 2-amino-5-R-thiazoles where R is a strong electron attractor. Ultraviolet spectra of a series of 2-amino-4-p-R-phenylthiazoles (12) and 2-amino-5-p-R-phenylthiazoles (13) were recorded in alcoholic solution (73), but, reported in an article on pK studies, remained undiscussed. Solvent effects on absorption spectra of 2-acetamido and 2-aminothiazoles have been studied (92). 

A bathochromic shift of about 5 nm results for the 320-nm band when a methyl substituent is introduced either in the 4- or 5-posiiion, The reverse is observed when the methyl is attached to nitrogen (56). Solvent effects on this 320-nm band suggest that in the first excited state A-4-thiazoline-2-thione is less basic than in the ground state (61). Ultraviolet spectra of a large series of A-4-thiazoline-2-thiones have been reported (60. 73). 

We now consider a type of analysis in which the data (which may consist of solvent properties or of solvent effects on rates, equilibria, and spectra) again are expressed as a linear combination of products as in Eq. (8-81), but now the statistical treatment yields estimates of both a, and jc,. This method is called principal component analysis or factor analysis. A key difference between multiple linear regression analysis and principal component analysis (in the chemical setting) is that regression analysis adopts chemical models a priori, whereas in factor analysis the chemical significance of the factors emerges (if desired) as a result of the analysis. We will not explore the statistical procedure, but will cite some results. We have already encountered examples in Section 8.2 on the classification of solvents and in the present section in the form of the Swain et al. treatment leading to Eq. (8-74). 

Solvatochromic pareuaeters, so called because they were Initially derived from solvent effects on UV/visible spectra, have been applied subsequently with success to a wide variety of solvent-dependent phenomena and have demonstrated good predictive ability. The B jo) scale of solvent polarity is based on the position of the intermolecular charge transfer absorption band of Reichardt s betaine dye [506]. Et(io> values are available for over 200 common solvents and have been used by Dorsey and co-%rarkers to study solvent interactions in reversed-phase liquid chromatography (section 4.5.4) [305,306]. For hydrogen-bonding solvents the... 

Iordanov TD, Davis JL, Masunov AE, Levenson A, Przhonska OV, Kachkovski AD (2009) Symmetry breaking in cationic polymethine dyes, part 1 ground state potential energy surfaces and solvent effects on electronic spectra of streptocyanines. Int J Quantum Chem 109 3592-3601... 

The least problematic issues are UV spectral changes as a function of different solvents between the reference and the test sample. Solvent effects on UV spectra in solvents of decreased dielectric constant compared with water parallel solvent effects on apparent pKa. The changes are most marked for acids, for example, leading to a numerical increase of up to two pKa units - an apparent decrease in the acidity of the carboxylic acid. Effects on bases are considerably less. The apparent pKa of a base in a reduced dielectric constant solvent might be up to about half a pKa unit numerically lower (less basic). The UV spectra of neutral compounds... 

The solvent effects on charge-transfer spectra between Me3Sn-NCS and I2 was investigated. Onsager s theory of dielectrics was used to estimate the stabilisation energy of excited states257. 

M. F. Nicol, Solvent effects on electronic spectra, Appl. Spect. Rev. 8 183 (1974). 

The several theoretical and/or simulation methods developed for modelling the solvation phenomena can be applied to the treatment of solvent effects on chemical reactivity. A variety of systems - ranging from small molecules to very large ones, such as biomolecules [236-238], biological membranes [239] and polymers [240] -and problems - mechanism of organic reactions [25, 79, 223, 241-247], chemical reactions in supercritical fluids [216, 248-250], ultrafast spectroscopy [251-255], electrochemical processes [256, 257], proton transfer [74, 75, 231], electron transfer [76, 77, 104, 258-261], charge transfer reactions and complexes [262-264], molecular and ionic spectra and excited states [24, 265-268], solvent-induced polarizability [221, 269], reaction dynamics [28, 78, 270-276], isomerization [110, 277-279], tautomeric equilibrium [280-282], conformational changes [283], dissociation reactions [199, 200, 227], stability [284] - have been treated by these techniques. Some of these... 

Zeng, J., Craw, J. S., Hush, N. S. and Reimers, J. R. Solvent effects on molecular and ionic spectra. 4. Photochemistry ofFe2+(H20)6 in water revisited possible mechanisms for the primacy absorption process leading to electron ejection,/. Phys. Chem., 98 (1994), 11075-11088... 

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