Totally avoided surface crossings in amino radical-radical recombinations
Abstract
Semi-empirically generated potential energy surfaces for NN bond rupture in hydrazine and NH bond rupture in ammonia show that ground-excited singlet state crossings or near crossings occur along certain geometrical pathways while other lower energy pathways exhibit no theoretical vestige of such a crossing. This latter observation is in agreement with experimental evidence indicating that NH 2 + NH 2 or NH 2 + H reactions occur without activation energies. Thus, while orbital or state symmetry arguments are useful qualitative guides as to the possible shape of surfaces along certain symmetry restricted pathways they provide no information for the non-symmetrical ones.
- Publication:
-
Chemical Physics Letters
- Pub Date:
- March 1976
- DOI:
- 10.1016/0009-2614(76)80029-2
- Bibcode:
- 1976CPL....38..516E
- Keywords:
-
- Amino Radical;
- Ammonolysis;
- Chemical Bonds;
- Hydrazines;
- Potential Energy;
- Propellant Decomposition;
- Recombination Reactions;
- Activation Energy;
- Dissociation;
- Molecular Energy Levels;
- Photodecomposition;
- Pyrolysis;
- Thermochemistry;
- Atomic and Molecular Physics