Are There π* Shape Resonances in Electron Scattering from Phosphate Groups?

Authors

Paul Burrow, University of Nebraska - LincolnFollow
Gordon A. Gallup, University of Nebraska - LincolnFollow
Alberto Modelli, Università di BolognaFollow

Date of this Version

2008

Citation

Published in Journal of Physical Chemistry A 2008, 112, pp 4106-4113

doi:10.1021/jp7109143

Comments

Copyright © 2008 American Chemical Society. Used by permission

Abstract

The temporary anion states of trimethyl phosphate and several compounds bearing the P=O group were explored using electron transmission spectroscopy and ab initio calculations to determine if these states have the characteristics of the π* resonances usually associated with multiple bonds. No evidence was found for this in (CH₃O)₃PO and, by extension, we do not expect them to appear in the phosphate group of DNA. Cl₃PO, however, does display such characteristics to some extent, and we show that they arise from the spatial properties of the π* (P-Cl) orbitals rather than from multiple PO bonding. A novel computational means to explore effects due to the relative size of a molecular orbital and that of the angular momentum barrier responsible for confining the additional electron is presented