A high‐resolution electron momentum spectroscopy and density functional theory study into the complete valence electronic structure of allene

Abstract

AbstractA study of the electronic structure of the complete valence shell of allene (1,2‐propadiene) is reported. New high‐resolution binding‐energy spectra were measured in the energy regime 6–34.5 eV over a range of different target electron momenta, so that momentum distributions (MDs) could be determined for each molecular orbital. These data supersede the low‐resolution work of Braidwood et al. [J Phys B 27 (1994) 2075–2087], and also clarify some ambiguities with the earlier results. Theoretical MDs were calculated using a plane wave impulse approximation (PWIA) model for the reaction mechanism and density functional theory (DFT) for the wave function. Three basis sets, at the local spin density (LSD) approximation level and, additionally, incorporating nonlocal corrections such as the generalized gradient approximation (GGA), were studied. A critical comparison between the experimental and theoretical MDs was made, and it allowed us to determine the “optimum” wave function for allene from the basis sets we considered. This wave function is then used to derive allene's chemically interesting molecular properties. A summary of some of these results and a comparison of them with those of other workers is also presented with the level of agreement typically being good. © 2001 John Wiley & Sons, Inc. J Comput Chem 22: 1321–1333, 2001