Comprehensive Experimental and Theoretical Study into the Complete Valence Electronic Structure of Norbornadiene
Date
2002
Authors
Mackenzie-Ross, H
Brunger, Michael J
Wang, Feng
Adcock, W
Maddern, T
Campbell, L.
Newell, W R
McCarthy, I E
Weigold, Erich
Appelbe, B
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Publisher
American Chemical Society
Abstract
Momentum Distributions (MDs), obtained using high-resolution electron momentum spectroscopy (HREMS), are reported for norbornadiene's 18 valence orbitals. Corresponding theoretical results, using generalized gradient approximation density functional theory (DFT) together with TZVP, DZVP, and DZVP2 basis functions and a plane wave impulse approximation to describe the ionization process, are also detailed. This work represents the first comprehensive HREMS/DFT investigation into the complete valence electronic structure of norbornadiene (NBD), with significant results being obtained. In particular, an exacting comparison between our experimental and theoretical MDs enables us to define the "optimum" basis for NBD, from those we studied. This "optimum" basis is then used to extract a wide range of NBD's important molecular property information, which are subsequently compared with the results of independent measurements and calculations. Agreement between our results and those from independent measurements was generally very good, highlighting the utility of HREMS in a priori basis set evaluation.
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Keywords
Keywords: Approximation theory; Binding energy; Chemical bonds; Electronic properties; Electronic structure; Green's function; Ground state; Ionization; Molecules; Nuclear magnetic resonance spectroscopy; Probability density function; Spectroscopy; Born-Opepenheime
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Source
Journal of Physical Chemistry A
Type
Journal article
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2037-12-31