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Title: Steric asymmetry and lambda-doublet propensities in state-to-state rotationally inelastic scattering of NO (2 pi 1/2) with He.

Abstract

Relative integrated cross sections are measured for rotationally inelastic scattering of NO({sup 2}{pi}{sub 1/2}), hexapole selected in the upper {Lambda}-doublet level of the ground rotational state (j = 0.5), in collisions with He at a nominal energy of 514 cm{sup -1}. Application of a static electric field E in the scattering region, directed parallel or antiparallel to the relative velocity vector v, allows the state-selected NO molecule to be oriented with either the N end or the O end towards the incoming He atom. Laser-induced fluorescence detection of the final state of the NO molecule is used to determine the experimental steric asymmetry, SA {triple_bond} ({sigma}{sub v}{up_arrow}{down_arrow}{sub E}-{sigma}{sub v}{up_arrow}{up_arrow}{sub E})/({sigma}{sub v}{up_arrow}{down_arrow}{sub E} + {sigma}{sub v}{up_arrow}{up_arrow}{sub E}), which is equal to within a factor of (-1) to the molecular steric effect, S{sub i {yields} f} {triple_bond} ({sigma}{sub He {yields} NO} - {sigma}{sub He {yields} ON})/({sigma}{sub He {yields} NO} + {sigma}{sub He {yields} ON}). The dependence of the integral inelastic cross section on the incoming {lambda}-doublet component is also observed as a function of the final rotational (j{prime}), spin-orbit ({Omega}{prime}), and {Lambda}-doublet ({epsilon}{prime}) state. The measured steric asymmetries are significantly larger than previously observed for NO-Ar scattering, supporting earlier proposals that themore » repulsive part of the interaction potential is responsible for the steric asymmetry. In contrast to the case of scattering with Ar, the steric asymmetry of NO-He collisions is not very sensitive to the value of {Omega}{prime} . However, the {Lambda}-doublet propensities are very different for [{Omega} = 0.5(F{sub 1}) {yields} {Omega}{prime} = 0.5(F{sub 1})] transitions. Spin-orbit manifold conserving collisions exhibit a propensity for parity conservation at low {Delta}{sub j}, but spin-orbit manifold changing collisions do not show this propensity. In conjunction with the experiments, state-to-state cross sections for scattering of oriented NO({sup 2}{pi}) molecules with He atoms are predicted from close-coupling calculations on restricted coupled-cluster methods including single, double, and noniterated triple excitations [J. Klos, G. Chalasinski, M. T. Berry, R. Bukowski, and S. M. Cybulski, J. Chem. Phys. 112, 2195 (2000)] and correlated electron-pair approximation [M. Yang and M. H. Alexander, J. Chem. Phys. 103, 6973 (1995)] potential energy surfaces. The calculated steric asymmetry S{sub i {yields} f} of the inelastic cross sections at E{sub tr} = 514 cm{sup -1} is in reasonable agreement with that derived from the present experimental measurements for both spin-manifold conserving (F{sub 1} {yields} F{sub 1}) and spin-manifold changing (F{sub 1} {yields} F{sub 2}) collisions, except that the overall sign of the effect is opposite. Additionally, calculated field-free integral cross sections for collisions at E{sub tr} = 508 cm{sup -1} are compared to the experimental data of Joswig et al. [J. Chem. Phys. 85, 1904 (1986)]. Finally, the calculated differential cross section for collision energy E{sub tr} = 491 cm{sup -1} is compared to experimental data of Westley et al. [J. Chem. Phys. 114, 2669 (2001)] for the spin-orbit conserving transition F{sub 1} (j = 0.5) {yields} F{sub 1}f(j{prime} = 3.5).« less

Authors:
 [1];  [1]; ;  [2];  [2]
  1. Vrije Universiteit, Amsterdam, The Netherlands
  2. University of Nijmegen, Nijmegen, The Netherlands
Publication Date:
Research Org.:
Sandia National Laboratories
Sponsoring Org.:
USDOE
OSTI Identifier:
964562
Report Number(s):
SAND2004-4029J
TRN: US0903873
DOE Contract Number:  
AC04-94AL85000
Resource Type:
Journal Article
Journal Name:
Proposed for publication in Journal of Chemical Physics.
Additional Journal Information:
Journal Name: Proposed for publication in Journal of Chemical Physics.
Country of Publication:
United States
Language:
English
Subject:
72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS; APPROXIMATIONS; ASYMMETRY; ATOMS; CROSS SECTIONS; DETECTION; DIFFERENTIAL CROSS SECTIONS; ELECTRIC FIELDS; FLUORESCENCE; HEXAPOLES; INELASTIC SCATTERING; INTEGRAL CROSS SECTIONS; PARITY; POTENTIAL ENERGY; ROTATIONAL STATES; SCATTERING; VECTORS; VELOCITY

Citation Formats

Wiskerke, Arjan E, de Lange, Marc J.L., Stolte, Steven, Taatjes, Craig A, van der Avoird, Ad, and Klos, Jacek. Steric asymmetry and lambda-doublet propensities in state-to-state rotationally inelastic scattering of NO (2 pi 1/2) with He.. United States: N. p., 2004. Web.
Wiskerke, Arjan E, de Lange, Marc J.L., Stolte, Steven, Taatjes, Craig A, van der Avoird, Ad, & Klos, Jacek. Steric asymmetry and lambda-doublet propensities in state-to-state rotationally inelastic scattering of NO (2 pi 1/2) with He.. United States.
Wiskerke, Arjan E, de Lange, Marc J.L., Stolte, Steven, Taatjes, Craig A, van der Avoird, Ad, and Klos, Jacek. Sun . "Steric asymmetry and lambda-doublet propensities in state-to-state rotationally inelastic scattering of NO (2 pi 1/2) with He.". United States.
@article{osti_964562,
title = {Steric asymmetry and lambda-doublet propensities in state-to-state rotationally inelastic scattering of NO (2 pi 1/2) with He.},
author = {Wiskerke, Arjan E and de Lange, Marc J.L. and Stolte, Steven and Taatjes, Craig A and van der Avoird, Ad and Klos, Jacek},
abstractNote = {Relative integrated cross sections are measured for rotationally inelastic scattering of NO({sup 2}{pi}{sub 1/2}), hexapole selected in the upper {Lambda}-doublet level of the ground rotational state (j = 0.5), in collisions with He at a nominal energy of 514 cm{sup -1}. Application of a static electric field E in the scattering region, directed parallel or antiparallel to the relative velocity vector v, allows the state-selected NO molecule to be oriented with either the N end or the O end towards the incoming He atom. Laser-induced fluorescence detection of the final state of the NO molecule is used to determine the experimental steric asymmetry, SA {triple_bond} ({sigma}{sub v}{up_arrow}{down_arrow}{sub E}-{sigma}{sub v}{up_arrow}{up_arrow}{sub E})/({sigma}{sub v}{up_arrow}{down_arrow}{sub E} + {sigma}{sub v}{up_arrow}{up_arrow}{sub E}), which is equal to within a factor of (-1) to the molecular steric effect, S{sub i {yields} f} {triple_bond} ({sigma}{sub He {yields} NO} - {sigma}{sub He {yields} ON})/({sigma}{sub He {yields} NO} + {sigma}{sub He {yields} ON}). The dependence of the integral inelastic cross section on the incoming {lambda}-doublet component is also observed as a function of the final rotational (j{prime}), spin-orbit ({Omega}{prime}), and {Lambda}-doublet ({epsilon}{prime}) state. The measured steric asymmetries are significantly larger than previously observed for NO-Ar scattering, supporting earlier proposals that the repulsive part of the interaction potential is responsible for the steric asymmetry. In contrast to the case of scattering with Ar, the steric asymmetry of NO-He collisions is not very sensitive to the value of {Omega}{prime} . However, the {Lambda}-doublet propensities are very different for [{Omega} = 0.5(F{sub 1}) {yields} {Omega}{prime} = 0.5(F{sub 1})] transitions. Spin-orbit manifold conserving collisions exhibit a propensity for parity conservation at low {Delta}{sub j}, but spin-orbit manifold changing collisions do not show this propensity. In conjunction with the experiments, state-to-state cross sections for scattering of oriented NO({sup 2}{pi}) molecules with He atoms are predicted from close-coupling calculations on restricted coupled-cluster methods including single, double, and noniterated triple excitations [J. Klos, G. Chalasinski, M. T. Berry, R. Bukowski, and S. M. Cybulski, J. Chem. Phys. 112, 2195 (2000)] and correlated electron-pair approximation [M. Yang and M. H. Alexander, J. Chem. Phys. 103, 6973 (1995)] potential energy surfaces. The calculated steric asymmetry S{sub i {yields} f} of the inelastic cross sections at E{sub tr} = 514 cm{sup -1} is in reasonable agreement with that derived from the present experimental measurements for both spin-manifold conserving (F{sub 1} {yields} F{sub 1}) and spin-manifold changing (F{sub 1} {yields} F{sub 2}) collisions, except that the overall sign of the effect is opposite. Additionally, calculated field-free integral cross sections for collisions at E{sub tr} = 508 cm{sup -1} are compared to the experimental data of Joswig et al. [J. Chem. Phys. 85, 1904 (1986)]. Finally, the calculated differential cross section for collision energy E{sub tr} = 491 cm{sup -1} is compared to experimental data of Westley et al. [J. Chem. Phys. 114, 2669 (2001)] for the spin-orbit conserving transition F{sub 1} (j = 0.5) {yields} F{sub 1}f(j{prime} = 3.5).},
doi = {},
journal = {Proposed for publication in Journal of Chemical Physics.},
number = ,
volume = ,
place = {United States},
year = {2004},
month = {8}
}