Vibrational spectra of methane clathrate hydrates from molecular dynamics simulation

Molecular dynamics simulations were performed on methane clathrate hydrates at ambient conditions. Thermal expansion results over the temperature range 60-300 K show that the unit cell volume increases with temperature in agreement with experiment. Power spectra were obtained at 273 K from velocity autocorrelation functions for selected atoms, and normal modes were assigned. The spectra were further classified according to individual atom types, allowing the assignment of contributions from methane molecules located in small and large cages within the structure I unit cell. The symmetric C-H stretch of methane in the small cages occurs at a higher frequency than for methane located in the large cages, with a peak separation of 14 cm(-1). Additionally, we determined that the symmetric C-H stretch in methane gas occurs at the same frequency as methane in the large cages. Results of molecular dynamics simulations indicate the use of power spectra obtained from the velocity autocorrelation function is a reliable method to investigate the vibrational behavior of guest molecules in clathrate hydrates.     

Influence of lattice interactions on the Jahn-Teller distortion of the [Cu(H2O)6]2+ ion: dependence of the crystal structure of K2[Cu(H2O)6](SO4)(2x)(SeO4)(2-2x) upon the sulfate/selenate ratio

The temperature dependence of the structure of the mixed-anion Tutton salt K2[Cu(H2O)6](SO4)(2x)(SeO4)(2-2x) has been determined for crystals with 0, 17, 25, 68, 78, and 100% sulfate over the temperature range of 85-320 K. In every case, the [Cu(H2O)6]2+ ion adopts a tetragonally elongated coordination geometry with an orthorhombic distortion. However, for the compounds with 0, 17, and 25% sulfate, the long and intermediate bonds occur on a different pair of water molecules from those with 68, 78, and 100% sulfate. A thermal equilibrium between the two forms is observed for each crystal, with this developing more readily as the proportions of the two counterions become more similar. Attempts to prepare a crystal with approximately equal amounts of sulfate and selenate were unsuccessful. The temperature dependence of the bond lengths has been analyzed using a model in which the Jahn-Teller potential surface of the [Cu(H2O)6]2+ ion is perturbed by a lattice-strain interaction. The magnitude and sign of the orthorhombic component of this strain interaction depends on the proportion of sulfate to selenate. Significant deviations from Boltzmann statistics are observed for those crystals exhibiting a large temperature dependence of the average bond lengths, and this may be explained by cooperative interactions between neighboring complexes.     

The Role of Organic Glasses in cis/trans Photoisomerization at Low Temperatures

Into the looking glass! Low temperature photoisomerization studies on some arenes have been studied in different organic glasses. The results are consistent with a possible softening of the glass and offer an explanation for the mechanism of photoisomerization in a confined medium.

     

Single-shot measurement of triplet-singlet relaxation in a Si/SiGe double quantum dot

We investigate the lifetime of two-electron spin states in a few-electron Si/SiGe double dot. At the transition between the (1,1) and (0,2) charge occupations, Pauli spin blockade provides a readout mechanism for the spin state. We use the statistics of repeated single-shot measurements to extract the lifetimes of multiple states simultaneously. When the magnetic field is zero, we find that all three triplet states have equal lifetimes, as expected, and this time is ~10 ms. When the field is nonzero, the T(0) lifetime is unchanged, whereas the T- lifetime increases monotonically with the field, reaching 3 sec at 1 T.