Solvent reorganization in optical and thermal electron-transfer processes: solvatochromism and intramolecular electron-transfer barriers in spheroidal molecules

Journal Article · Thu Aug 27 04:00:00 EDT 1987 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100302a017· OSTI ID:6091189

Brunschwig, B S; Ehrenson, S; Sutin, N

Expressions for the shift of the absorption and emission band maxima of a solute with changes of the solvent's dielectric properties are presented for solute molecules with shapes and polarizabilities that can be approximated by those of spherical dielectric-continuum cavity. The derivations use a nonequilibrium thermodynamic approach developed by Marcus. An series of accurate approximations for the solvent shifts are presented. The new expressions are shown to reduce to equations previously derived by McRae, Ooshika, Mataga, and others when point-dipole approximations are made and particular values of the solute polarizability are assigned. The polarizability of the solute can be related to the internal dielectric constant of the cavity, and general expressions for the band shift in the point-dipole limit containing the dielectric constant of the cavity as a parameter are derived.

• Research Organization: Brookhaven National Lab., Upton, NY
• DOE Contract Number: AC02-76CH00016
• OSTI ID: 6091189
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 91:18; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
CHEMICAL REACTIONS
DATA
DIPOLE MOMENTS
ELECTRON TRANSFER
ELECTRONIC STRUCTURE
ENERGY
FREE ENTHALPY
INFORMATION
NUMERICAL DATA
PHOTOCHEMICAL REACTIONS
PHYSICAL PROPERTIES
SOLUTES
SOLVENT PROPERTIES
SOLVENTS
THEORETICAL DATA
THERMODYNAMIC PROPERTIES
THERMODYNAMICS