ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
Ab initio molecular orbital calculations up to the coupled-cluster level with the aug-cc-pVQZ basis set allowed us to have a new look at the electron affinity of nitrous oxide (N2O) resulting in a detection of a new N2O− entity, and thereby a novel mechanism for the dissociative electron attachment process, N2O+e−→N2+O−. Addition of an electron to the linear N2O ground state (X 1Σ+) leads first to an open-chain bound anion which lies 25 kJ/mol above the neutral. Upon a cyclization of the open anion with an additional energy barrier of 25 kJ/mol, a cyclic anionic species is formed which is more stable than the open isomer and lies now, at most, 3 kJ/mol above the neutral ground state (the transition structure for cyclization being 50 kJ/mol above neutral N2O). The cyclic anionic species constitutes a weak complex between N2 and O− characterized by a binding energy of only 16 kJ/mol. The electronic structure of the anion complex is analyzed, a number of earlier experimental results are clarified and a resolution for the long-standing disagreement between experiment and theory around the electron affinity of N2O is proposed. © 2001 American Institute of Physics.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.1364679
