C. William McCurdy

PROGRESS IN THE APPLICATION OF CLASSICAL S-MATRIX THEORY TO INELASTIC COLLISION PROCESSES

Methods are described which effectively solve two of the technical difficulties associated with applying classical S‐matrix theory to inelastic/reactive scattering. Specifically, it is shown that rather standard numerical methods can be used to solve the ’’root search’’ problem (i.e., the nonlinear boundary value problem necessary to impose semiclassical quantum conditions at the beginning and the end of the classical trajectories) and also how complex classical trajectories, which are necessary to describe classically forbidden (i.e., tunneling) processes, can be computed in a numerically stable way. Application is made to vibrational relaxation of H2 by collision with He (within the helicity conserving approximation). The only remaining problem with regard to applying classical S‐matrix theory to complex collision processes has to do with the availability of multidimensional uniform asymptotic formulas for interpolating the ’’primitive’’ semiclassical expressions between their various regions of validity.

Second order Moller-Plesset and coupled cluster singles and doubles methods with complex basis functions for resonances in electron-molecule scattering

The method of complex basis functions is applied to molecular resonances at correlated levels of theory. Møller-Plesset perturbation theory at second order and equation-of-motion electron attachment coupled-cluster singles and doubles (EOM-EA-CCSD) methods based on a non-Hermitian self-consistent-field reference are used to compute accurate Siegert energies for shape resonances in small molecules including N2-, CO-, CO2-, and CH2O-. Analytic continuation of complex 𝜃-trajectories is used to compute Siegert energies, and the 𝜃-trajectories of energy differences are found to yield more consistent results than those of total energies. The ability of such methods to accurately compute complex potential energy surfaces is investigated, and the possibility of using EOM-EA-CCSD for Feshbach resonances is explored in the context of e-helium scattering.

Implementation of the CCGM approximation for surface diffraction using Wigner R-matrix theory

The CCGM approximation for surface scattering proposed by Cabrera, Celli, Goodman, and Manson [Surf. Sci. 19, 67 (1970)] is implemented for realistic surface interaction potentials using Wigner R‐matrix theory. The resulting procedure is highly efficient computationally and is in no way limited to hard wall or purely repulsive potentials. Comparison is made with the results of close‐coupling calculations of other workers which include the same diffraction channels in order to fairly evaluate the CCGM approximation which is an approximation to the coupled channels Lippman–Schwinger equation for the T matrix. The shapes of selective adsorption features, whether maxima or minima, in the scattered intensity are well represented in this approach for cases in which the surface corrugation is not too strong.

Current status and future perspectives of electron interactions with molecules, clusters, surfaces, and interfaces [Workshop on Fundamental challenges in electron-driven chemistry; Workshop on Electron-driven processes: Scientific challenges and technological opportunities]

This report is based largely on presentations and discussions at two workshops and contributions from workshop participants. The workshop on Fundamental Challenges in Electron-Driven Chemistry was held in Berkeley, October 9-10, 1998, and addressed questions regarding theory, computation, and simulation. The workshop on Electron-Driven Processes: Scientific Challenges and Technological Opportunities was held at Stevens Institute of Technology, March 16-17, 2000, and focused largely on experiments. Electron-molecule and electron-atom collisions initiate and drive almost all the relevant chemical processes associated with radiation chemistry, environmental chemistry, stability of waste repositories, plasma-enhanced chemical vapor deposition, plasma processing of materials for microelectronic devices and other applications, and novel light sources for research purposes (e.g. excimer lamps in the extreme ultraviolet) and in everyday lighting applications. The life sciences are a rapidly advancing field where the important role of electron-driven processes is only now beginning to be recognized. Many of the applications of electron-initiated chemical processes require results in the near term. A large-scale, multidisciplinary and collaborative effort should be mounted to solve these problems in a timely way so that their solution will have the needed impact on the urgent questions of understanding the physico-chemical processes initiated and driven by electron interactions.