Thermochemistry of N-N containing ions: a threshold photoelectron photoion coincidence spectroscopy study of ionized methyl- and tetramethylhydrazine

The Journal of Physical Chemistry. a
Anne-Marie BoulangerPaul M Mayer

Abstract

The unimolecular dissociation reactions of the methylhydrazine (MH) and tetramethylhydrazine (TMH) radical cations have been investigated using tandem mass spectrometry and threshold photoelectron photoion coincidence spectroscopy in the photon energy ranges 9.60-31.95 eV (for the MH ion) and 7.74-29.94 eV (for the TMH ion). Methylhydrazine ions (CH3NHNH2(+*)) have three low-energy dissociation channels: hydrogen atom loss to form CH2NHNH2(+) (m/z 45), loss of a methyl radical to form NHNH2(+) (m/z 31), and loss of methane to form the fragment ion m/z 30, N2H2(+*). Tetramethylhydrazine ions only exhibit two dissociation reactions near threshold: that of methyl radical loss to form (CH3)2NNCH3(+) (m/z 73) and of methane loss to form the fragment ion m/z 72 with the empirical formula C3H8N2(+*). The experimental breakdown curves were modeled with Rice-Ramsperger-Kassel-Marcus theory, and it was found that, particularly for methyl radical loss, variational transition state theory was needed to obtain satisfactory fits to the data. The 0 K enthalpies of formation (delta(f)H0) for all fragment ions (m/z 73, m/z 72, m/z 45, m/z 31, and m/z 30) have been determined from the 0 K activation energies (E0) obtained from the fitting proced...Continue Reading

References

Apr 16, 2003·Accounts of Chemical Research·Stephen J Blanksby, G Barney Ellison
Jul 11, 2006·The Journal of Physical Chemistry. a·Anne-Marie BoulangerPaul M Mayer
Jun 2, 2007·The Journal of Physical Chemistry. a·Anne-Marie BoulangerPaul M Mayer

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Citations

Oct 18, 2008·Journal of the American Society for Mass Spectrometry·Anne-Marie BoulangerPaul M Mayer
Jun 14, 2013·The Journal of Chemical Physics·Fabian HolzmeierIngo Fischer
Jul 21, 2011·Mass Spectrometry Reviews·Guy Bouchoux, Jean-Yves Salpin
Dec 17, 2009·The Journal of Physical Chemistry. a·Paul M MayerDavid A Shaw
Sep 25, 2009·The Journal of Physical Chemistry. a·Paul M MayerDavid A Shaw
Jul 9, 2021·The Journal of Physical Chemistry. a·Xiao-Bo LiWei-Qun Shi

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