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Title: Communication: The origin of rotational enhancement effect for the reaction of H{sub 2}O{sup +} + H{sub 2} (D{sub 2})

We have measured the absolute integral cross sections (σ’s) for H{sub 3}O{sup +} formed by the reaction of rovibrationally selected H{sub 2}O{sup +}(X{sup 2}B{sub 1}; v{sub 1}{sup +}v{sub 2}{sup +}v{sub 3}{sup +} = 000; N{sup +}{sub Ka}{sup +}{sub Kc}{sup +} = 0{sub 00}, 1{sub 11}, and 2{sub 11}) ion with H{sub 2} at the center-of-mass collision energy (E{sub cm}) range of 0.03–10.00 eV. The σ(0{sub 00}), σ(1{sub 11}), and σ(2{sub 11}) values thus obtained reveal rotational enhancements at low E{sub cm} < 0.50 eV, in agreement with the observation of the previous study of the H{sub 2}O{sup +}(X{sup 2}B{sub 1}) + D{sub 2} reaction. This Communication presents important progress concerning the high-level ab initio quantum calculation of the potential energy surface for the H{sub 2}O{sup +}(X{sup 2}B{sub 1}) + H{sub 2} (D{sub 2}) reactions, which has provided valuable insight into the origin of the rotational enhancement effect. Governed by the charge and dipole-induced-multipole interactions, the calculation shows that H{sub 2} (D{sub 2}) approaches the H end of H{sub 2}O{sup +}(X{sup 2}B{sub 1}) in the long range, whereas chemical force in the short range favors the orientation of H{sub 2} (D{sub 2}) toward the O side of H{sub 2}O{sup +}. Themore » reorientation of H{sub 2}O{sup +} reactant ion facilitated by rotational excitation thus promotes the H{sub 2}O{sup +} + H{sub 2} (D{sub 2}) reaction along the minimum energy pathway, rendering the observed rotational enhancement effects. The occurrence of this effect at low E{sub cm} indicates that the long range charge and dipole-induced-multipole interactions of the colliding pair play a significant role in the dynamics of the exothermic H{sub 2}O{sup +} + H{sub 2} (D{sub 2}) reactions.« less
Authors:
; ;  [1] ;  [2] ; ; ; ;  [3]
  1. Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131 (United States)
  2. Department of Biology and Chemistry, City University of Hong Kong, Kowloon (Hong Kong)
  3. Department of Chemistry, University of California, Davis, California 95616 (United States)
Publication Date:
OSTI Identifier:
22253659
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 140; Journal Issue: 1; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; COLLISIONS; EXCITATION; HYDROGEN; INTEGRAL CROSS SECTIONS; INTERACTIONS; NITROGEN IONS; OXONIUM IONS; POTENTIAL ENERGY; WATER