The Extent of Non–Born-Oppenheimer Coupling in the Reaction of Cl( 2 P ) with para- H 2-Reference-Cited by-同舟云学术

The Extent of Non–Born-Oppenheimer Coupling in the Reaction of Cl( 2 P ) with para- H 2

Published:2008-10-24 Issue:5901 Volume:322 Page:573-576
ISSN:0036-8075
Container-title:Science
language:en
Short-container-title:Science

Author:

Wang Xingan¹²³⁴⁵,Dong Wenrui¹²³⁴⁵,Xiao Chunlei¹²³⁴⁵,Che Li¹²³⁴⁵,Ren Zefeng¹²³⁴⁵,Dai Dongxu¹²³⁴⁵,Wang Xiuyan¹²³⁴⁵,Casavecchia Piergiorgio¹²³⁴⁵,Yang Xueming¹²³⁴⁵,Jiang Bin¹²³⁴⁵,Xie Daiqian¹²³⁴⁵,Sun Zhigang¹²³⁴⁵,Lee Soo-Y.¹²³⁴⁵,Zhang Dong H.¹²³⁴⁵,Werner Hans-Joachim¹²³⁴⁵,Alexander Millard H.¹²³⁴⁵

Affiliation:

1. State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning 116023, People's Republic of China.

2. Institute of Theoretical and Computational Chemistry, Key Laboratory of Mesoscopic Chemistry of Ministry of Education, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, People's Republic of China.

3. Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371, Singapore.

4. School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371, Singapore.

5. Institute für Theoretische Chemie, Universität Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart, Germany.

Abstract

Elementary triatomic reactions offer a compelling test of our understanding of the extent of electron-nuclear coupling in chemical reactions, which is neglected in the widely applied Born-Oppenheimer (BO) approximation. The BO approximation predicts that in reactions between chlorine (Cl) atoms and molecular hydrogen, the excited spin-orbit state (Cl*) should not participate to a notable extent. We report molecular beam experiments, based on hydrogen-atom Rydberg tagging detection, that reveal only a minor role of Cl*. These results are in excellent agreement with fully quantum-reactive scattering calculations based on two sets of ab initio potential energy surfaces. This study resolves a previous disagreement between theory and experiment and confirms our ability to simulate accurately chemical reactions on multiple potential energy surfaces.

Publisher

American Association for the Advancement of Science (AAAS)

Subject

Multidisciplinary

Reference34 articles.

1. T. C. Allisonet al., in Gas-Phase Chemical Reaction Systems: Experiments and Models 100 Years After Max Bodenstein, J. Wolfrum, H.-R. Volpp, R. Rannacher, J. Warnatz, Eds. (Springer, Heidelberg, Germany, 1996), pp. 111–124.

2. Dynamics of the Simplest Chlorine Atom Reaction: An Experimental and Theoretical Study

3. P. Casavecchia, Rep. Prog. Phys.63, 355 (2000).

4. K. J. Laidler, Chemical Kinetics (Harper and Row, New York, 1987), pp. 14, 288–298.

5. Theoretical Study of the Validity of the Born-Oppenheimer Approximation in the Cl + H 2 → HCl + H Reaction

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