Spectroscopic signatures of halogens in clathrate hydrate cages. 2. Iodine.

UV-vis and Raman spectroscopy were used to study iodine molecules trapped in sII clathrate hydrate structures stabilized by THF, CH(2)Cl(2), or CHCl(3). The spectra show that the environment for iodine inside the water cage is significantly less perturbed than either in aqueous solution or in amorphous water-ice. The resonance Raman progression of I(2) in THF clathrate hydrate can be observed up to v = 6 when excited at 532 nm.

Spectroscopic signatures of halogens in clathrate hydrate cages. 1. Bromine.

We report the first UV-vis spectroscopic study of bromine molecules confined in clathrate hydrate cages. Bromine in its natural hydrate occupies 51262 and 51263 lattice cavities. Bromine also can be encapsulated into the larger 51264 cages of a type II hydrate formed mainly from tetrahydrofuran or dichloromethane and water.

Vibrational dissipation and dephasing of I2 (v = 1-19) in solid Kr.

Time- and frequency-resolved coherent anti-Stokes Raman scattering is used to carry out systematic measurements of vibrational dephasing on I2 (v = 1-19) isolated in solid Kr, as a function of temperature, T = 7-45 K. The observed quantum beats, omega(v', v") allow an accurate reconstruction of the solvated molecular potential, which is well represented by the Morse form: omega(e) = 211.56 +/- 0.

High-resolution electron spin resonance spectroscopy of XeF* in solid argon. The hyperfine structure constants as a probe of relativistic effects in the chemical bonding properties of a heavy noble gas atom.

Xenon fluoride radicals were generated by solid-state chemical reactions of mobile fluorine atoms with xenon atoms trapped in Ar matrix. Highly resolved electron spin resonance spectra of XeF* were obtained in the temperature range of 5-25 K and the anisotropic hyperfine parameters were determined for magnetic nuclei 19F, 129Xe, and 131Xe using naturally occurring and isotopically enriched xenon. Signs of parallel and perpendicular hyperfine components were established from analysis of temperature changes in the spectra and from numerical solutions of the spin Hamiltonian for two nonequivalent magnetic nuclei.