Abstract
We have measured the absolute integral cross sections (σ's) for H3O+ formed by the reaction of rovibrationally selected H2O+(X2B1; v1+v2+v3+ = 000; N+Ka+Kc+ = 000, 111, and 211) ion with H2 at the center-of-mass collision energy (Ecm) range of 0.03-10.00 eV. The σ(000), σ(111), and σ(211) values thus obtained reveal rotational enhancements at low Ecm <0.50 eV, in agreement with the observation of the previous study of the H2O+(X2B1) + D2 reaction. This Communication presents important progress concerning the high-level ab initio quantum calculation of the potential energy surface for the H2O+(X2B1) + H2 (D2) 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 H2 (D2) approaches the H end of H2O+(X2B1) in the long range, whereas chemical force in the short range favors the orientation of H2 (D2) toward the O side of H2O+. The reorientation of H2O+ reactant ion facilitated by rotational excitation thus promotes the H2O+ + H2 (D2) reaction along the minimum energy pathway, rendering the observed rotational enhancement effects. The occurrence of this effect at low Ecm 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 H2O+ + H2 (D2) reactions. © 2014 AIP Publishing LLC.
| Original language | English |
|---|---|
| Article number | 011102 |
| Journal | Journal of Chemical Physics |
| Volume | 140 |
| Issue number | 1 |
| Online published | 6 Jan 2014 |
| DOIs | |
| Publication status | Published - 7 Jan 2014 |
Publisher's Copyright Statement
- COPYRIGHT TERMS OF DEPOSITED FINAL PUBLISHED VERSION FILE: This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing. This article appeared in Anyang Li, Yongle Li, Hua Guo, Kai-Chung Lau, Yuntao Xu, Bo Xiong, Yih-Chung Chang, and C. Y. Ng , "Communication: The origin of rotational enhancement effect for the reaction of H2O+ + H2 (D2)", J. Chem. Phys. 140, 011102 (2014) and may be found at https://doi.org/10.1063/1.4861002.