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No Access Submitted: 24 July 2017 Accepted: 07 September 2017 Published Online: 27 September 2017

  • Non-adiabatic behavior in the homolytic and heterolytic bond dissociation of protonated hydrazine: A guided ion beam and theoretical investigation
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J. Chem. Phys. 147, 124306 (2017); https://doi.org/10.1063/1.4997415
Christopher P. McNary and P. B. Armentrouta)
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  • Christopher P. McNary
  • P. B. Armentrout
ABSTRACT
Threshold collision-induced dissociation using a guided ion beam tandem mass spectrometer was performed on protonated hydrazine and its perdeuterated variant. The dominant dissociation pathways observed were endothermic homolytic and heterolytic cleavages of the N–N bond. The data were analyzed using a statistical model after accounting for internal and kinetic energy distributions, multiple collisions, and kinetic shifts to obtain 0 K bond dissociation energies. Comparison with literature thermochemistry demonstrates that both channels behave non-adiabatically. Heterolytic bond cleavage yields NH2+ + NH3 products, but the NH2+ fragment is in the spin-restricted excited 1A1 state and not in the spin-forbidden ground 3B1 state, whereas homolytic bond cleavage leads to dissociation to the NH3+ + NH2 product asymptote with NH2 in its excited 2A1 state rather than the energetically favored 2B1 state. The rationale for the non-adiabatic behavior observed in the homolytic bond cleavage is revealed by detailed theoretical calculations of the relevant potential energy surfaces and the relevant occupied valence molecular orbitals. These calculations suggest that the non-adiabatic behavior results from conservation of the σ and π character of the binding and lone pair electrons on the nitrogen atoms.

ACKNOWLEDGMENTS

This work was supported by the National Science Foundation, Grant Nos. CHE-1359769 and CHE-1664618, with partial support from ENSCO, Inc. We thank the Center of High Performance Computing at the University of Utah for the generous allocation of computer time and the Extreme Science and Engineering Discovery Environment (XSEDE), Grant No. TG-CHE170012, for allocations on the large shared-memory cluster at Pittsburgh Supercomputing Center at Carnegie Mellon University.
The authors declare no competing financial interest.

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