Rudolph, H. and McKoy, V. and Dixit, S. N. (1989) Rotational branching ratios at low photoelectron energies in resonant enhanced multiphoton ionization of NO. Journal of Chemical Physics, 90 (5). pp. 2570-2574. ISSN 0021-9606 http://resolver.caltech.edu/CaltechAUTHORS:20120530-142259771
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We report calculated rotational branching ratios for very low energy (50 meV) photoelectrons resulting from (1+1′) resonant enhanced multiphoton ionization (REMPI) via the J_i =1/2, 3/2, 5/2, and 7/2 levels of the P_(11) branch of the A ^2Σ^+ (3sσ) state of NO. Even angular momentum transfer (ΔN≡N_+−N_i) peaks are dominant in these rotational distributions, in agreement with the selection rule ΔN+l=odd. Angular momentum coupling in the photoelectron wave function arising from the molecular ion potential leads to smaller but appreciable ΔN=odd peaks. The calculated ΔN=0 to ΔN=+2 peak ratios show the same strong decrease when J_i increases from 1/2 to 3/2 as seen in the experimental zero‐kinetic‐energy (ZEKE) photoelectron spectra [Sander et al., Phys. Rev. A 36, 4543 (1987)], but do not show the rapid die‐off of the ΔN≠0 peaks for higher J_i observed experimentally. The calculated trend in the ΔN=+2 vs ΔN=0 peaks could be understood on the basis of simple angular momentum transfer arguments. These same arguments indicate that this trend in the ΔN=0 and +2 peaks with increasing angular momentum is not generally expected in other branches. Spectra via the R_(21) ( J) branch are presented to support this assertion. We also present photoelectron angular distributions which show a strong dependence on ΔN reflecting the changing composition of the photoelectron wave function.
|Additional Information:||© 1989 American Institute of Physics. Received 13 July 1988; accepted 18 November 1988. This material is based on research supported by the National Science Foundation under Grant No. CHE-8521391, by AFOSR under Grant No. 87-0039, and by the Office of Health and Environmental Research of DOE (DE-FG03- 87ER60513). The authors also acknowledge use of the resources of the San Diego SuperComputer Center which is supported by the National Science Foundation. Work done by S.N.D. was performed under the auspices of the U.S. Department of Energy by Lawrence Livermore National Laboratory under Contract No. W-7405-Eng-48. H.R. gratefully acknowledges the support of the Danish Natural Science Research Council.|
|Subject Keywords:||NITRIC OXIDE, PHOTOELECTRON SPECTROSCOPY, PHOTOIONIZATION, MULTI−PHOTON PROCESSES, BRANCHING RATIO, ROTATIONAL STATES|
|Classification Code:||PACS: 33.80.Rv; 33.60.+q; 33.20.Sn|
|Official Citation:||Rotational branching ratios at low photoelectron energies in resonant enhanced multiphoton ionization of NO H. Rudolph, V. McKoy, and S. N. Dixit J. Chem. Phys. 90, 2570 (1989); http://dx.doi.org/10.1063/1.455953|
|Usage Policy:||No commercial reproduction, distribution, display or performance rights in this work are provided.|
|Deposited By:||Ruth Sustaita|
|Deposited On:||30 May 2012 22:03|
|Last Modified:||26 Dec 2012 15:17|
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