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Photoion rotational distributions from near-threshold to deep in the continuum

Poliakoff, E. D. and Choi, Heung Cheun and Rao, R. M. and Mihill, A. G. and Kakar, Sandeep and Wang, Kwanghsi and McKoy, V. (1995) Photoion rotational distributions from near-threshold to deep in the continuum. Journal of Chemical Physics, 103 (5). pp. 1773-1787. ISSN 0021-9606. doi:10.1063/1.469751.

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We present the first measurements of ion rotational distributions for photoionization over an extended range [0 ≤ E_K ≤ 200 eV for N_2 (2σ^(−1)_u ) and 3 ≤ E_K ≤ 125 eV for CO (4σ^(−1))]. The N_2 ion rotational distributions are seen to change dramatically over this energy range, indicating that characteristically molecular behavior of the photoelectron persists far from ionization threshold. In addition, the N_2 and CO results show a strikingly different dependence on energy. Although differences are expected due to the absence of a center of symmetry in CO, detailed calculations reveal that this behavior arises from the presence of Cooper minima in the 2σ_u →kσ_g continuum in the case of N_2 and from an f‐wave shape resonance in the 4σ→kσ channel in CO. Agreement between measured and calculated ion rotational distributions is excellent. The N_2 results are also compared with electron bombardment ionization data. This comparison demonstrates that previous interpretations of electron bombardment data are prone to errors.

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Additional Information:© 1995 American Institute of Physics. (Received 6 March 1995; accepted 24 April 1995) The efforts of the CAMD staff are greatly appreciated and we are particularly indebted to Dr. Volker Saile, Dr. John Scott, and Dr. Eizi Morikawa for their support with the plane grating monochromator. We are also indebted to Professor Roger Stockbauer for many helpful discussions. E.D.P. acknowledges support from NSF (CHE-9315857) and the Louisiana LEQSF program. Work at the California Institute of Technology was supported by grants from the Air Force Office of Scientific Research and the Office of Health and Environmental Research of the U.S. 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 Physics9055
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ID Code:61270
Deposited By: George Porter
Deposited On:21 Oct 2015 14:55
Last Modified:10 Nov 2021 22:46

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