UV Photodissociation Action Spectroscopy of Haloanilinium Ions in a Linear Quadrupole Ion Trap Mass Spectrometer

American Chemical Society (ACS) - Tập 24 - Trang 932-940 - 2013
Christopher S. Hansen1,2, Benjamin B. Kirk1,2, Stephen J. Blanksby1,2, Richard. A. J. O’Hair3,4, Adam J. Trevitt1,2
1School of Chemistry, University of Wollongong, Wollongong, Australia
2ARC Centre of Excellence for Free Radical Chemistry and Biotechnology, Wollongong, Australia
3School of Chemistry, The University of Melbourne, Melbourne, Australia
4ARC Centre of Excellence for Free Radical Chemistry and Biotechnology, Melbourne, Australia

Tóm tắt

UV–vis photodissociation action spectroscopy is becoming increasingly prevalent because of advances in, and commercial availability of, ion trapping technologies and tunable laser sources. This study outlines in detail an instrumental arrangement, combining a commercial ion-trap mass spectrometer and tunable nanosecond pulsed laser source, for performing fully automated photodissociation action spectroscopy on gas-phase ions. The components of the instrumentation are outlined, including the optical and electronic interfacing, in addition to the control software for automating the experiment and performing online analysis of the spectra. To demonstrate the utility of this ensemble, the photodissociation action spectra of 4-chloroanilinium, 4-bromoanilinium, and 4-iodoanilinium cations are presented and discussed. Multiple photoproducts are detected in each case and the photoproduct yields are followed as a function of laser wavelength. It is shown that the wavelength-dependent partitioning of the halide loss, H loss, and NH3 loss channels can be broadly rationalized in terms of the relative carbon-halide bond dissociation energies and processes of energy redistribution. The photodissociation action spectrum of (phenyl)Ag2 + is compared with a literature spectrum as a further benchmark.

Tài liệu tham khảo

Rohr, M.I.S., Petersen, J., Brunet, C., Antoine, R., Broyer, M., Dugourd, P., Bonacic-Koutecky, V., O'Hair, R.A.J., Mitric, R.: Synthesis and spectroscopic characterization of diphenylargentate, (C6H5)2Ag-. J. Phys. Chem. Lett. 3(9), 1197–1201 (2012)

Brunet, C., Antoine, R., Broyer, M., Dugourd, P., Kulesza, A., Petersen, J., Rohr, M.I.S., Mitric, R., Bonacic-Koutecky, V., O'Hair, R.A.J.: Structural and photochemical properties of organosilver reactive intermediates MeAg2 + and PhAg2 +. J. Phys. Chem. A 115(33), 9120–9127 (2011)

Mitric, R., Petersen, J., Kulesza, A., Rohr, M.I.S., Bonacic-Koutecky, V., Brunet, C., Antoine, R., Dugourd, P., Broyer, M., O'Hair, R.A.J.: Gas-phase synthesis and vibronic action spectroscopy of Ag2H+. J. Phys. Chem. Lett. 2(6), 548–552 (2011)

Dehmelt, H.G., Jefferts, K.B.: Alignment of the H2 + Molecular ion by selective photodissociation. I. Phys. Rev. 125(4), 1318–1322 (1962)

Richardson, C.B., Jefferts, K.B., Dehmelt, H.G.: Alignment of the H2 molecular ion by selective photodissociation. II. Experiments on the radio-frequency spectrum. Phys. Rev. 165(1), 80–87 (1968)

Dunbar, R.C.: Photodissociation of CH3Cl+ and N2O+ cations. J. Am. Chem. Soc. 93(18), 4354–4358 (1971)

Dunbar, R.C. In: Gas Phase Ion Chemistry; Vol. 2. Bowers, M.T. Ed., Ed. Academic Press: New York; pp. 181–220 (1979)