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Photoion Alignment: Chemical Signatures 200 eV above Threshold

Das, Romith and Wu, Chuanyong and Mihill, A. G. and Poliakoff, E. D. and Wang, Kwanghsi and McKoy, V. (1995) Photoion Alignment: Chemical Signatures 200 eV above Threshold. Journal of Physical Chemistry, 99 (6). pp. 1741-1747. ISSN 0022-3654. doi:10.1021/j100006a016.

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We present results of experiment and theory for the alignment of CO^+(B^2Σ^+) and N_2^+(B^2Σ^+_u) photoions over an extended energy range (0 ≤ E_k ≤ 210 eV for CO and 0 ≤ E_k ≤ 250 eV for N_2). The polarization of CO^+(B^2Σ^+ → X^2Σ^+) and N_2^+(B^2Σ^+ → X^2Σ^+_g) fluorescence is used to interpret the oscillator strength distributions for normally unresolved degenerate ionization channels. The results show the influence of a CO 4σ → kσ shape resonance clearly and agreement between theory and experiment is excellent. However, agreement between the calculated and measured values is less satisfactory for N_2. This behavior is somewhat surprising, as previous rotationally resolved fluorescence experiments have shown excellent agreement between theory and experiment. This comparison helps to illustrate the complementarity of alignment studies relative to alternative probes of ionization. For both N_2 and CO, the data indicate that the photoions retain significant alignment even at high energies. The results demonstrate that even well above threshold the spectral dependence of the alignment (i.e., polarization) is very sensitive to the molecular environment for photoejection. Such behavior provides useful insight into fundamental scattering phenomena in chemical physics.

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Additional Information:© 1995 American Chemical Society. Received: August 24, 1994; In Final Form: September 26, 1994. The efforts of the CAMD staff are greatly appreciated and we are particularly indebted to Drs. Volker Saile, John Scott, and Eizi Morikawa for their support. E.D.P. acknowledges support from NSF (CHE-9315857) and the Louisiana LEQSF program. Work at the California Institute of Technology was supported by the Air Force Office of Scientific Research and the Office of Health and Environmental Research of the US. Department of Energy. We also acknowledge use of resources of the Jet Propulsion Laboratory/Caltech Cray Y-MP2E/232 supercomputer.
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Louisiana LEQSF programUNSPECIFIED
Air Force Office of Scientific Research (AFOSR)UNSPECIFIED
Department of Energy (DOE)UNSPECIFIED
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Caltech Arthur Amos Noyes Laboratory of Chemical Physics8977
Issue or Number:6
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Official Citation:Photoion Alignment: Chemical Signatures 200 eV above Threshold Romith Das, Chuanyong Wu, A. G. Mihill, E. D. Poliakoff, Kwanghsi Wang, and V. McKoy The Journal of Physical Chemistry 1995 99 (6), 1741-1747 DOI: 10.1021/j100006a016
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:61273
Deposited By: George Porter
Deposited On:20 Oct 2015 20:59
Last Modified:10 Nov 2021 22:46

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