Herman-Wallis correction in vibrational CARS of oxygen
Light molecules are subject to vibration–rotation (VR) interaction, which implies corrections to the rigid rotor approximation and, in particular, corrections to spectral line intensities are related to the so‐called Herman–Wallis (HW) factor. This problem is outlined here for the spectral response...
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| Published in | Journal of Raman spectroscopy Vol. 42; no. 10; pp. 1836 - 1842 |
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| Main Author | |
| Format | Journal Article |
| Language | English |
| Published |
Chichester, UK
John Wiley & Sons, Ltd
01.10.2011
Wiley Subscription Services, Inc |
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| Online Access | Get full text |
| ISSN | 0377-0486 1097-4555 1097-4555 |
| DOI | 10.1002/jrs.2965 |
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| Abstract | Light molecules are subject to vibration–rotation (VR) interaction, which implies corrections to the rigid rotor approximation and, in particular, corrections to spectral line intensities are related to the so‐called Herman–Wallis (HW) factor. This problem is outlined here for the spectral response of some medium‐weight diatomics in the gas phase and probed by means of vibrational coherent anti‐Stokes Raman scattering (CARS) used for diagnostic reasons in combustion science. However, different from other works on this subject, we specialized our analysis to oxygen and, since the peculiarity of its anti‐bonding molecular orbital, we find that the VR coupling is responsible for deviations that compete with the effect of Raman line widths typical of collisional environments of hot gases at room pressure. The HW correction is ultimately demonstrated to affect O2 CARS thermometry in such a manner that the accuracy for measurements at high temperatures can be improved. Copyright © 2011 John Wiley & Sons, Ltd.
Vibration‐rotation interaction generates corrections to spectral line intensities. Such problem is here outlined for the spectral response of some medium‐weight diatomics in the gas phase and probed by means of vibrational coherent anti‐Stokes Raman scattering (CARS). Emphasis is on oxygen for the peculiarity of its anti‐bonding molecular orbital. |
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| AbstractList | Light molecules are subject to vibration–rotation (VR) interaction, which implies corrections to the rigid rotor approximation and, in particular, corrections to spectral line intensities are related to the so‐called Herman–Wallis (HW) factor. This problem is outlined here for the spectral response of some medium‐weight diatomics in the gas phase and probed by means of vibrational coherent anti‐Stokes Raman scattering (CARS) used for diagnostic reasons in combustion science. However, different from other works on this subject, we specialized our analysis to oxygen and, since the peculiarity of its anti‐bonding molecular orbital, we find that the VR coupling is responsible for deviations that compete with the effect of Raman line widths typical of collisional environments of hot gases at room pressure. The HW correction is ultimately demonstrated to affect O
2
CARS thermometry in such a manner that the accuracy for measurements at high temperatures can be improved. Copyright © 2011 John Wiley & Sons, Ltd. Light molecules are subject to vibration-rotation (VR) interaction, which implies corrections to the rigid rotor approximation and, in particular, corrections to spectral line intensities are related to the so-called Herman-Wallis (HW) factor. This problem is outlined here for the spectral response of some medium-weight diatomics in the gas phase and probed by means of vibrational coherent anti-Stokes Raman scattering (CARS) used for diagnostic reasons in combustion science. However, different from other works on this subject, we specialized our analysis to oxygen and, since the peculiarity of its anti-bonding molecular orbital, we find that the VR coupling is responsible for deviations that compete with the effect of Raman line widths typical of collisional environments of hot gases at room pressure. The HW correction is ultimately demonstrated to affect O2 CARS thermometry in such a manner that the accuracy for measurements at high temperatures can be improved. Light molecules are subject to vibration-rotation (VR) interaction, which implies corrections to the rigid rotor approximation and, in particular, corrections to spectral line intensities are related to the so-called Herman-Wallis (HW) factor. This problem is outlined here for the spectral response of some medium-weight diatomics in the gas phase and probed by means of vibrational coherent anti-Stokes Raman scattering (CARS) used for diagnostic reasons in combustion science. However, different from other works on this subject, we specialized our analysis to oxygen and, since the peculiarity of its anti-bonding molecular orbital, we find that the VR coupling is responsible for deviations that compete with the effect of Raman line widths typical of collisional environments of hot gases at room pressure. The HW correction is ultimately demonstrated to affect O2 CARS thermometry in such a manner that the accuracy for measurements at high temperatures can be improved. Copyright © 2011 John Wiley & Sons, Ltd. [PUBLICATION ABSTRACT] Light molecules are subject to vibration–rotation (VR) interaction, which implies corrections to the rigid rotor approximation and, in particular, corrections to spectral line intensities are related to the so‐called Herman–Wallis (HW) factor. This problem is outlined here for the spectral response of some medium‐weight diatomics in the gas phase and probed by means of vibrational coherent anti‐Stokes Raman scattering (CARS) used for diagnostic reasons in combustion science. However, different from other works on this subject, we specialized our analysis to oxygen and, since the peculiarity of its anti‐bonding molecular orbital, we find that the VR coupling is responsible for deviations that compete with the effect of Raman line widths typical of collisional environments of hot gases at room pressure. The HW correction is ultimately demonstrated to affect O2 CARS thermometry in such a manner that the accuracy for measurements at high temperatures can be improved. Copyright © 2011 John Wiley & Sons, Ltd. Vibration‐rotation interaction generates corrections to spectral line intensities. Such problem is here outlined for the spectral response of some medium‐weight diatomics in the gas phase and probed by means of vibrational coherent anti‐Stokes Raman scattering (CARS). Emphasis is on oxygen for the peculiarity of its anti‐bonding molecular orbital. |
| Author | Marrocco, Michele |
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| Cites_doi | 10.1366/000370277774463625 10.1002/jrs.2201 10.1063/1.1730279 10.1021/jp960412n 10.1016/0010-4655(86)90233-X 10.1117/12.7972754 10.1364/AO.40.000741 10.1007/978-94-009-1620-3_18 10.1016/S0022-2852(02)00012-7 10.1016/S0022-4073(01)00014-0 10.1063/1.1742069 10.1016/0022-4073(76)90097-2 10.1103/PhysRev.41.721 10.1017/CBO9780511814808 10.1016/0022-2852(87)90108-1 10.1016/0584-8539(95)01631-7 10.1364/OL.10.000478 10.1063/1.2410237 10.1016/j.optcom.2007.09.040 10.1063/1.462116 10.1063/1.467803 10.1016/j.pecs.2009.11.001 10.1063/1.1535443 10.1002/jrs.2662 10.1016/j.cplett.2007.05.103 10.1002/jrs.1250150109 10.1016/j.proci.2008.06.045 10.1002/0470845767 10.1016/0079-6727(81)90002-1 10.1016/0010-2180(79)90006-3 |
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| Notes | ArticleID:JRS2965 This article is part of the Journal of Raman Spectroscopy special issue entitled "Proceedings of the 9th European Conference on Nonlinear Optical Spectroscopy (ECONOS), Bremen, Germany, June 21-23, 2010" edited by Peter Radi, PSI, Villigen, Switzerland, and Arnulf Materny, Jacobs University, Bremen, Germany. ark:/67375/WNG-RRDBP93G-R istex:CF6B9C925D56D66FFBC36392FEAA168C25381DE3 th This article is part of the Journal of Raman Spectroscopy special issue entitled “Proceedings of the 9 European Conference on Nonlinear Optical Spectroscopy (ECONOS), Bremen, Germany, June 21‐23, 2010” edited by Peter Radi, PSI, Villigen, Switzerland, and Arnulf Materny, Jacobs University, Bremen, Germany. ObjectType-Article-1 SourceType-Scholarly Journals-1 ObjectType-Feature-2 content type line 14 ObjectType-Article-2 ObjectType-Feature-1 content type line 23 |
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| Snippet | Light molecules are subject to vibration–rotation (VR) interaction, which implies corrections to the rigid rotor approximation and, in particular, corrections... Light molecules are subject to vibration-rotation (VR) interaction, which implies corrections to the rigid rotor approximation and, in particular, corrections... |
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| SubjectTerms | Approximation Cars coherent anti-Stokes Raman scattering Combustion Coupling (molecular) Deviation High temperature laser spectroscopy Mathematical analysis Raman scattering spectroscopic techniques Virtual reality |
| Title | Herman-Wallis correction in vibrational CARS of oxygen |
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