Anharmonic RRKM Calculation for the Dissociation of (H2O)(2)H+ and Its Deuterated Species (D2O)(2)D+
文献类型：期刊论文
| 作者 | Song, Di1,2; Su, Hongmei1; Kong, Fan-ao1; Lin, Sheng-Hsien2,3 |
| 刊名 | JOURNAL OF PHYSICAL CHEMISTRY A
 |
| 出版日期 | 2010-09-23 |
| 卷号 | 114期号:37页码:10217-10224 |
| ISSN号 | 1089-5639 |
| DOI | 10.1021/jp103782r |
| 英文摘要 | Investigations on the dissociation kinetics of hydrated protonium ions, (H2O)(2)H+ and their deuterated species (H2O)(2)D+, are reported based on the harmonic and anharmonic oscillator model using the transition state theory and ab initio calculations. We find that the dissociation of (H2O)(2)H+ and (D2O)(2)D+ exhibits a distinct threshold behavior due to the existence of activation energies. Moreover, the deviation between the harmonic and anharmonic dissociation rate constants becomes larger in the high energy or temperature range, with the rate constants becoming unreasonably large under the harmonic oscillator model. The isotope effect is found to become more distinct but only in the case of the anharmonic oscillator model. These results show that the anharmonic Rice-Ramsperger-Kassel-Marcus (RRKM) theory can provide a reasonably good description for the dissociation of (H2O)(2)H+ and (D2O)(2)D+. Furthermore, a theoretical model to demonstrate the principle of vibrational predissociation spectroscopy (VPS) is established from the viewpoint of RRKM theory and applied in determining the experimental conditions and understanding the role of the dissociation rate constant k(E) played in the VPS experiment, using (H2O)(2)H+ and (H2O)(2)D+ as examples. |
| 语种 | 英语 |
| WOS记录号 | WOS:000281753800032 |
| 出版者 | AMER CHEMICAL SOC |
| 源URL | [http://ir.iccas.ac.cn/handle/121111/70451]  |
| 专题 | 中国科学院化学研究所 |
| 通讯作者 | Song, Di |
| 作者单位 | 1.Chinese Acad Sci, Inst Chem, BNLMS, Beijing 100190, Peoples R China 2.Natl Chiao Tung Univ, Inst Appl Chem, Inst Mol Sci, Hsinchu 30050, Taiwan 3.Acad Sinica, Inst Atom & Mol Sci, Taipei, Taiwan |
| 推荐引用方式 GB/T 7714 | Song, Di,Su, Hongmei,Kong, Fan-ao,et al. Anharmonic RRKM Calculation for the Dissociation of (H2O)(2)H+ and Its Deuterated Species (D2O)(2)D+[J]. JOURNAL OF PHYSICAL CHEMISTRY A,2010,114(37):10217-10224. |
| APA | Song, Di,Su, Hongmei,Kong, Fan-ao,&Lin, Sheng-Hsien.(2010).Anharmonic RRKM Calculation for the Dissociation of (H2O)(2)H+ and Its Deuterated Species (D2O)(2)D+.JOURNAL OF PHYSICAL CHEMISTRY A,114(37),10217-10224. |
| MLA | Song, Di,et al."Anharmonic RRKM Calculation for the Dissociation of (H2O)(2)H+ and Its Deuterated Species (D2O)(2)D+".JOURNAL OF PHYSICAL CHEMISTRY A 114.37(2010):10217-10224. |
入库方式： OAI收割
来源：化学研究所
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