Photofragment spectroscopy and dynamics of NiOH+ and NiOH+(H2O)

Christopher J. Thompson, Fernando Aguirre, John Husband, Ricardo B. Metz

Research output: Contribution to journalArticle

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Abstract

Photodissociation of thermalized NiOH+ and NiOH+(H2O) are examined over the visible and near-ultraviolet using time-of-flight mass spectrometry. Branching ratios and photodissociation cross sections are monitored as a function of laser wavelength. Loss of OH is the only dissociation channel observed in NiOH+, whereas loss of H2O and OH are present, and competitive, in the photodissociation of NiOH+(H2O). The photofragmentspectrum of NiOH+ shows absorption bands at ∼300 and ∼400 nm. An almost identical spectrum is observed for the net photodissociation of NiOH+(H2O). Spectroscopic thresholds taken from the photofragment spectra have been corrected to yield upper limits to the 0 K bond energies for the ions: D°0(Ni+-OH) ≤ 271 ± 9 kJ/mol, D°0(NiOH+-H2O) ≤ 271 ± 9 kJ/mol, and D°0(Ni+H2O-OH) ≤ 334 ± 5 kJ/mol. Calculated B3LYP values are consistent with the experimental upper limits, but suggest that the true D°0(NiOH+-H2O) and D°0(Ni+H2O-OH) lie significantly below these upper limits. Photodissociation of NiOH+(H2O) near 300 nm leads to greater OH production than RRKM calculations predict, suggesting that excitation in this region leads to direct Ni+-OH bond cleavage.

Original languageEnglish
Pages (from-to)9901-9905
Number of pages5
JournalJournal of Physical Chemistry A
Volume104
Issue number44
Publication statusPublished - Nov 9 2000

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Photodissociation
photodissociation
Spectroscopy
spectroscopy
Mass spectrometry
Absorption spectra
cleavage
mass spectroscopy
dissociation
Ions
absorption spectra
Wavelength
thresholds
Lasers
cross sections
wavelengths
excitation
lasers
ions

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Thompson, C. J., Aguirre, F., Husband, J., & Metz, R. B. (2000). Photofragment spectroscopy and dynamics of NiOH+ and NiOH+(H2O). Journal of Physical Chemistry A, 104(44), 9901-9905.

Photofragment spectroscopy and dynamics of NiOH+ and NiOH+(H2O). / Thompson, Christopher J.; Aguirre, Fernando; Husband, John; Metz, Ricardo B.

In: Journal of Physical Chemistry A, Vol. 104, No. 44, 09.11.2000, p. 9901-9905.

Research output: Contribution to journalArticle

Thompson, CJ, Aguirre, F, Husband, J & Metz, RB 2000, 'Photofragment spectroscopy and dynamics of NiOH+ and NiOH+(H2O)', Journal of Physical Chemistry A, vol. 104, no. 44, pp. 9901-9905.
Thompson, Christopher J. ; Aguirre, Fernando ; Husband, John ; Metz, Ricardo B. / Photofragment spectroscopy and dynamics of NiOH+ and NiOH+(H2O). In: Journal of Physical Chemistry A. 2000 ; Vol. 104, No. 44. pp. 9901-9905.
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