Comprehensive Experimental and Theoretical Study into the Complete Valence Electronic\nStructure of Norbornadiene

Abstract

Momentum Distributions (MDs), obtained using high-resolution electron momentum spectroscopy (HREMS),\nare reported for norbornadiene's 18 valence orbitals. Corresponding theoretical results, using generalized\ngradient approximation density functional theory (DFT) together with TZVP, DZVP, and DZVP2 basis\nfunctions and a plane wave impulse approximation to describe the ionization process, are also detailed. This\nwork represents the first comprehensive HREMS/DFT investigation into the complete valence electronic\nstructure of norbornadiene (NBD), with significant results being obtained. In particular, an exacting comparison\nbetween our experimental and theoretical MDs enables us to define the “optimum” basis for NBD, from\nthose we studied. This “optimum” basis is then used to extract a wide range of NBD's important molecular\nproperty information, which are subsequently compared with the results of independent measurements and\ncalculations. Agreement between our results and those from independent measurements was generally very\ngood, highlighting the utility of HREMS in a priori basis set evaluation.