Index of content:
Volume 118, Issue 19, 15 May 2003
118(2003); http://dx.doi.org/10.1063/1.1573171View Description Hide Description
Ab initio calculations have been performed to obtain the polarizability of water clusters up to It is shown that a simple linear relation involving the aggregation number fits the polarizability results extremely well (with correlation coefficient indicating a near additive nature of this quantity for weakly bonded molecular clusters. Calculated dynamic polarizabilities are also shown to follow the same trend. The effect of electron correlation on the static polarizability of water clusters has also been investigated.
Exact solution (within a triple-zeta, double polarization basis set) of the electronic Schrödinger equation for water118(2003); http://dx.doi.org/10.1063/1.1574318View Description Hide Description
Using a newly developed density matrix renormalization group algorithm, we have computed exact solutions of the Schrödinger equation for water at two geometries in a basis of 41 orbitals. Calculations of this size cannot be carried out using any other method. We compare our results with high-order coupled cluster and configuration interaction calculations.
118(2003); http://dx.doi.org/10.1063/1.1574018View Description Hide Description
The hydration shell of ion in the gas phase is smaller than that in solution (6). The energetics of various solvated clusters indicate that lowering the pairwise interaction between the ligand and the ion can increase the coordination number in the gas phase. We report here the first hexa-coordinated cluster ion in the gas phase, which can be formed by substituting with 1,4-difluorobenzene. Infrared-photodissociation spectroscopy of the O–H stretch was used to infer the structure.
118(2003); http://dx.doi.org/10.1063/1.1573635View Description Hide Description
The coupling of the tunneling- and proton dipolar reservoirs of a weakly hindered methyl group is used to dynamically polarize the rare-spin nuclei by combination with suitable radio-frequency irradiation schemes. and double-resonance experiments below 60 K in a pure γ-picoline matrix and with 1.5 % as a guest are reported at a field of 5.17 Tesla.
118(2003); http://dx.doi.org/10.1063/1.1574801View Description Hide Description
It has recently been suggested that the lifetime of the lowest triplet state in multiphoton-excited is much longer than anticipated. If true, this would invalidate the assumption of internal thermal equilibrium in the description of statistical decay processes of the molecule, such as thermionic emission. We present pump–probe measurements which show that the lifetime is below 1 μs at vibrational excitation energies of 6.5 eV, and that it decreases further to 40 ns at 10 eV.