Volume 113, Issue 2, 08 July 2000
Index of content:
113(2000); http://dx.doi.org/10.1063/1.481821View Description Hide Description
We have performed the fs pump–probe experiment on the nonadiabatic transition in the Hg–CO vdW complex. It is found that the transition occurs near the point where Hg and CO come nearest to each other on the -state surface with a probability of 0.07 for their single encounter. This experiment serves as the first observation of the wave packet dynamics associated with an intermolecular energy flow in the vdW interaction.
Theoretical analysis of singlet–triplet energy splitting generated by charge-transfer interaction in electron donor–acceptor radical pair systems113(2000); http://dx.doi.org/10.1063/1.481823View Description Hide Description
A theoretical analysis was performed for a prediction of the singlet–triplet energy splitting (J) of electron donor–acceptor radical pairs on the basis of the electron transferreactiontheory. It has been strongly indicated that charge-transfer interaction dominates the J in condensed phase photoinduced electron transfer systems.
Different acoustic wave effects of thickness-extension and thickness-shear mode resonance oscillation on catalytic activity and selectivity of thin Pd and Ag films deposited on ferroelectric single crystals113(2000); http://dx.doi.org/10.1063/1.481824View Description Hide Description
The two representative vibration modes, thickness-extension and thickness-shear, of resonance oscillation were employed to examine the effects of lattice vibration of acoustic waves on the activity and the selectivity of catalytic reactions. Thickness-extension mode resonance oscillation dramatically increased the activity of acetaldehyde production in ethanoloxidation on Pd and enhanced the selectivity for ethylene production in ethanol decomposition on Ag; only ethylene production was accelerated without changes in acetaldehyde production. On the other hand, thickness-shear mode resonance oscillation promoted neither oxidation nor decomposition of ethanol. From the comparison of lattice displacement, large lattice displacement vertical to the surface is shown to be useful for the activation of catalysis by the metal surfaces.
Ab initio computation of forces and molecular spectroscopic constants using plane waves based auxiliary field Monte Carlo with application to113(2000); http://dx.doi.org/10.1063/1.481825View Description Hide Description
Correlated sampling within the shifted contour auxiliary field Monte Carlo method, implemented using plane waves and pseudopotentials, allows computation of electronic forces on nuclei, potential energy differences, geometric and vibrotational spectroscopic constants. This is exemplified on the molecule, where it is demonstrated that it is possible to accurately compute forces, dissociation energies, bond length parameters, and harmonic frequencies.