The coordination of photosensitizing Ru(II) dyes to a nanocrystalline titania film, as employed in the Gratzel solar cell, has been examined by vibrational spectroscopy. The major infrared bands of the adsorbed dyes have been assigned by comparison with spectra (IR and Raman) of the parent dye molecules, and suggest a bidentate chelate or bridging coordination to the TiO2 surface via two carboxylate groups per dye molecule.

Vibrational Spectroscopic Study of the Coordination of (2,2‘-Bipyridyl-4,4‘-dicarboxylic acid)ruthenium(II) Complexes to the Surface of Nanocrystalline Titania

The heat capacities of glassy and liquid toluene and ethylbenzene were measured with an adiabatic calorimeter. Both samples were doped with about 10% of benzene to suppress crystallization. The effects of the doping were corrected for by assuming the additivity of the heat capacities of toluene (or ethylbenzene) and benzene. The configurational entropies of several glass-forming liquids, including toluene and ethylbenzene, were calculated as functions of temperature from their heat-capacity data. For these calculations, the vibrational heat capacities were determined by the least-squares fitting of the Debye and Einstein functions to the experimental values using auxiliary spectroscopic data from the literature. The size of cooperative rearranging region (CRR), which was first conceived by Adam and Gibbs, was calculated from the configurational entropy in a simplifying approximation that neglects distribution of CRR size and internal entropy of CRR. For all of the systems examined, the size of CRR increas...

Calorimetric Study of Glassy and Liquid Toluene and Ethylbenzene: Thermodynamic Approach to Spatial Heterogeneity in Glass-Forming Molecular Liquids†

Vibrational spectra of monosubstituted pyridines

The formation and decay of parent negative ions have been studied with electron‐swarm and electron‐beam techniques. The rate of attachment at thermal energies under electron‐swarm conditions for SF6 and C6H5NO2 was determined to be 1.24×109 and 2.1×107 sec−1·torr−1, respectively. Autoionization lifetimes for SF6−, C6H5NO2−, and (CH3CO)2− are reported to be 25, 40, and 12 μsec, respectively. The absolute rate of electron attachment in SF6 was found to be independent of the temperature (298°≤T≤418°K), and is thus consistent with an electron capture cross section for SF6 which varies inversely with the speed of the electron. The attachment rates and lifetimes were combined through the principle of detailed balance to calculate the ratio of density of states of the negative ion to that of the neutral plus electron. A simple theoretical treatment of long‐lived negative ions is presented, and the possibility of estimating electron affinities from measurements of attachment cross sections and negative‐ion lifeti...

J.H.S. Green

Papers

Vibrational spectra of monosubstituted pyridines

The vibrational spectra of benzene derivatives—I. Nitrobenzene, the benzoate ion, alkali metal benzoates and salicylates

Vibrational spectra of benzene derivatives-III. Anisole, ethylbenzene, phenetole methyl phenyl sulphide and ethyl phenyl sulphide

Vibrational spectra of benzene derivatives—II: Assignment and calculated thermodynamic functions for benzonitrile

Far infra-red spectroscopy of benzene derivatives