6.2.2. Definition of Effective Properties 3064 6.3. Response Properties to Magnetic Fields 3066 6.3.1. Nuclear Shielding 3066 6.3.2. Indirect Spin−Spin Coupling 3067 6.3.3. EPR Parameters 3068 6.4. Properties of Chiral Systems 3069 6.4.1. Electronic Circular Dichroism (ECD) 3069 6.4.2. Optical Rotation (OR) 3069 6.4.3. VCD and VROA 3070 7. Continuum and Discrete Models 3071 7.1. Continuum Methods within MD and MC Simulations 3072

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Quantum mechanical continuum solvation models.

6. Rehybridization of the Acceptor (RICT) 3908 7. Planarization of the Molecule (PICT) 3909 III. Fluorescence Spectroscopy 3909 A. Solvent Effects and the Model Compounds 3909 1. Solvent Effects on the Spectra 3909 2. Steric Effects and Model Compounds 3911 3. Bandwidths 3913 4. Isoemissive Points 3914 B. Dipole Moments 3915 C. Radiative Rates and Transition Moments 3916 1. Quantum Yields and Radiationless Deactivation Processes 3916

Structural Changes Accompanying Intramolecular Electron Transfer: Focus on Twisted Intramolecular Charge-Transfer States and Structures

▪ Abstract Proton-coupled electron transfer (PCET) is an important mechanism for charge transfer in a wide variety of systems including biology- and materials-oriented venues. We review several are...

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Proton-Coupled Electron Transfer

Implicit Solvation Models: Equilibria, Structure, Spectra, and Dynamics.

Time-resolved emission measurements of the solute coumarin 153 (C153) are used to probe the time dependence of solvation in 24 common solvents at room temperature. Significant improvements in experimental time resolution ({approx}100 fs instrument response) as well as corresponding improvements in analysis methods provide confidence that all of the spectral evolution (including both the inertial and the diffusive parts of the response) are observed in these measurements. Extensive data concerning the steady-state solvatochromism of C153, coupled to an examination of the effects of vibrational relaxation, further demonstrate that the spectral dynamics being observed accurately monitor the dynamics of nonspecific solvation. Comparisons to theoretical predictions show that models based on the dielectric response of the pure solvent provide a semiquantitative understanding of the dynamics observed. 156 refs., 26 figs., 5 tabs.

Subpicosecond Measurements of Polar Solvation Dynamics: Coumarin 153 Revisited

Steady-state and time-resolved emission measurements of the solvatochromic probe coumarin 153 are used to study solvation of a dipolar solute in nondipolar solvents such as benzene and 1,4-dioxane. Contrary to the predictions of dielectric continuum theories, the Stokes shifts (or nuclear reorganization energies) that accompany electronic excitation of this solute are substantial in such solvents (∼1000 cm-1). The magnitudes of the shifts observed in both nondipolar and dipolar solvents can be consistently understood in terms of the relative strength of the interactions between the permanent charge distributions of the solute and solvent molecules. (Information concerning these charge distributions is derived from extensive ab initio calculations on the solute and 31 common solvents.) The dynamics of solvation in nondipolar solvents, as reflected in the time dependence of the Stokes shifts, is qualitatively like that observed in polar solvents. But, whereas the dynamics in polar solvents can be rather sim...

Dipole Solvation in Nondipolar Solvents: Experimental Studies of Reorganization Energies and Solvation Dynamics†

Subpicosecond fluorescence anisotropy measurements are used to characterize the rotational dynamics of coumarin 153 (C153) in 35 common solvents and eight solvent mixtures at room temperature. The rotational anisotropy decays of C153 are generally nonexponential as a result of the non-Markovian nature of the friction on its rotational motion. Rotational correlation times are observed to be larger in polar solvents than in nonpolar solvents of the same viscosity. This difference is examined in the context of theories of dielectric friction, which relate the extra friction in polar solute/solvent systems to long-range dipole -dipole interactions. Since the latter interactions have been thoroughly characterized via dynamic Stokes shift measurements for the same solute/solvent combinations studied here, the present data provide a unique opportunity to test general concepts of dielectric friction. Contrary to expectations, the departures from simple hydrodynamic behavior cannot be modeled using only theories of rotational dielectric friction. More important than dielectric friction is the role that the relative solute/solvent size plays in determining the extent of solute -solvent coupling. Once this size dependence is approximately accounted for, the remaining departures from simple hydrodynamic behavior are relatively small in all solvents. In polar aprotic solvents, solvation data indicate that dielectric friction effects should be rather modest (10-20% of the total friction). In these solvents no clear correlation is found between dielectric friction predictions and the observed solute -solvent coupling. However, in normal alcohol solvents the effects of dielectric friction are predicted to be large and well beyond the scatter in the experimental data. No evidence for such an important dielectric friction contribution is observed in these solvents, in spite of the fact that long-time components of the solvation dynamics do appear to be present in the rotational friction.

Rotational Dynamics of Coumarin 153: Time-Dependent Friction, Dielectric Friction, and Other Nonhydrodynamic Effects

The excited-state dynamics of polymer-bound J-aggregates formed in aqueous mixtures of pseudoisocyanine (PIC) chloride and poly(vinyl sulfonic acid sodium salt) (PVS) (MW≃11 200) have been studied by picosecond time-correlated single-photon counting and picosecond polarized pump-probe spectroscopy. At a concentration of 40 μM PIC and 5×10 -4 g/dL PVS, the absorption spectrum of the J-aggregate is characterized by a J-band at 565 nm with a fwhm of ≃500 cm -1 . For this particular mixture, a dye molecule is bound to each of the SO 3 - groups on the polymer chains. The physical size of the aggregate is therefore determined by the number of polymer residues (≃87) per chain

Miin Liang Horng

Papers

Subpicosecond Measurements of Polar Solvation Dynamics: Coumarin 153 Revisited

Dipole Solvation in Nondipolar Solvents: Experimental Studies of Reorganization Energies and Solvation Dynamics†

Rotational Dynamics of Coumarin 153: Time-Dependent Friction, Dielectric Friction, and Other Nonhydrodynamic Effects

Excited-state dynamics of polymer-bound J-aggregates

Picosecond spectroscopic studies of electronic energy relaxation in H-aggregates of 1,1'-diethyl-2,2'-dicarbocyanine on colloidal silica