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Chen E.S.,Baylor College of Medicine | Herder C.,Massachusetts Institute of Technology | Keith H.,Wentworth Foundation | Chen E.C.M.,University of Houston-Clear Lake
Journal of Theoretical and Computational Chemistry | Year: 2010

Hund's state conservation rule predicts (1 × 6) [N (4S) + O(-)(2P)] plus 9 × 9 [(3P) N(-) + O(3P)] = 87 spin states for NO(-). The experimental Ea(NO), 0.92(2)-0.16(2) eV are assigned to the (3 + 27) bonding states with anion bond orders, 0.80-1.15. The Ea(NO) 0.026(5)-0.14(2) eV are assigned to seven of the 27 nonbonding states with anion bond orders about one. The negative E a(NO) for the 20 other nonbonding and 30 antibonding states are estimated. Ionic Morse potentials are calculated for 87 predicted states for NO(-) and the 54 bonding and antibonding states of superoxide. © 2010 World Scientific Publishing Company. Source


Chen E.S.,Baylor College of Medicine | Chen E.C.M.,Wentworth Foundation | Chen E.C.M.,University of Houston-Clear Lake | Rosenthal R.,Wentworth Foundation | And 5 more authors.
Rapid Communications in Mass Spectrometry | Year: 2016

Rationale Superoxide is the most significant homonuclear diatomic anion in biochemistry. Theory predicts 12 doublet (X, A-K) and 12 quartet (a-l) electronic states split by spin orbital coupling into 54 states dissociating to the 3P(O) + 2P(O-) limit. Dissociation energies for the 27 bonding states with positive electron affinities have been determined from mass spectrometric data. However, the 27 antibonding states with negative electron affinities have not been experimentally characterized. Methods The electron affinity of the hydrogen atom per electron, the Hylleraas, is the fundamental measure of electron correlation. It has been used to assign and evaluate experimental electron affinities of atoms and diatomic molecules. The 27 negative electron affinities of oxygen are estimated from the 27 positive values and the Hylleraas. These values are used to determine frequencies and internuclear separations by fitting theoretical electron impact distributions to the gas-phase mass spectrometric atomic oxygen anion distribution peaking at about 6.5 eV. Results The dissociation energies, internuclear distances and frequencies giving the first complete set of Morse potential energy curves for the 54 superoxide states dissociating to the lowest limit are reported from mass spectrometric data. The potentials are compared to theoretical and empirical literature curves. Conclusions The existence of the 27 bonding and 27 antibonding spin orbital coupling superoxide states dissociating to 3P(O) + 2P(O-) is established from mass analyzed thermal, photon, and electron ionization data. There are electron affinities from 0 to 0.15 eV, and onsets and peaks for dissociative electron attachment that cannot be explained by the 54 states. These support the existence of the 36 superoxide spin states dissociating to [1D(O) + 2P(O-)] and [1S(O) + 2P(O-)] predicted by quantum mechanics. © 2016 John Wiley & Sons, Ltd. Source


Chen E.S.,Baylor College of Medicine | Keith H.,Wentworth Foundation | Lim T.,Wentworth Foundation | Pham D.,Wentworth Foundation | And 8 more authors.
Journal of Molecular Modeling | Year: 2015

Theoretical adiabatic electron affinities are often considered inaccurate because they are referenced to only a single value. Ground state electron affinities for all the main group elements and homonuclear diatomics were identified recently using the normalized binding energy of the hydrogen atom: [0.75420375(3)/2 = 0.37710187(1) eV]. Here we revisit experimental values and extend the identifications to diatomics in the G2-1 set. We assign new ground state electron affinities: (eV) Cl2, 3.2(2); Br2, 2.87(14); CH, 2.1(2); H2, 0.6 ; NH, 1.1, SiH, 1.90. Anion Morse potentials are calculated for H2 and N2 from positive electron affinities and for hyperfine superoxide states for the first time. © 2015, Springer-Verlag Berlin Heidelberg. Source

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