High resolution electron momentum spectroscopy of the valence orbitals of water

Abstract

The development of a third-generation electron momentum spectrometer with significantly improved energy and momentum resolutions at Tsinghua University (Delta E = 0.45-0.68 eV, Delta theta = +/- 0.53 degrees and Delta phi = +/- 0.84 degrees) has enabled a reinvestigation of the valence orbital electron momentum distributions of H(2)Owith improved statistical accuracy. The measurements have been conducted at impact energies of 1200 eV and 2400 eV in order to check the validity of the plane wave impulse approximation. The obtained ionization spectra and electron momentum distributions have been compared with the results of computations carried out with Hartree Fock [HF] theory, density functional theory in conjunction with the standard B3LYP functional, one-particle Green's function [1-GF] theory along with the third-order algebraic diagrammatic construction scheme [ADC(3)], symmetry adapted cluster configuration interaction [SAC-Cl] theory, and a variety of multi-reference [MR-SDCI, MR-RSPT2, MR-RSPT3] theories. The influence of the basis set on the computed momentum distributions has been investigated further, using a variety of basis sets ranging from 6-31 G to the almost complete d-aug-cc-pV6Z basis set. A main issue in the present work pertains to a shake-up band of very weak intensity at 27.1 eV, of which the related momentum distribution was analyzed for the first time. The experimental evidences and the most thorough theoretical calculations demonstrate that this band borrows its ionization intensity from the 2a(1)orbital. (C) 2007 Elsevier B.V. All rights reserved.