Theoretical Proton Affinity and Fluoride Affinity of Nerve Agent VX

被引:6
|
作者
Bera, Narayan C. [1 ,2 ]
Maeda, Satoshi [1 ,2 ]
Morokuma, Keiji [1 ,2 ]
Viggiano, Al A. [3 ]
机构
[1] Emory Univ, Cherry L Emerson Ctr Sci Computat, Atlanta, GA 30322 USA
[2] Emory Univ, Dept Chem, Atlanta, GA 30322 USA
[3] USAF, Res Lab, Space Vehicles Directorate, Hanscom AFB, MA 01731 USA
来源
JOURNAL OF PHYSICAL CHEMISTRY A | 2010年 / 114卷 / 50期
关键词
IONIZATION MASS-SPECTROMETRY; ION-MOLECULE REACTIONS; 298; K; SOLVOLYSIS; CHEMISTRY; KINETICS; ACID; HNO3;
D O I
10.1021/jp107718w
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Proton affinity and fluoride affinity of nerve agent VX at all of its possible sites were calculated at the RI-MP2/cc-pVTZ//B3LYP/6-31G* and RI-MP2/aug-cc-pVTZ//B3LYP/6-31+G* levels, respectively. The protonation leads to various unique structures, with H+ attached to oxygen, nitrogen, and sulfur atoms; among which the nitrogen site possesses the highest proton affinity of -Delta E similar to 251 kcal/mol, suggesting that this is likely to be the major product. In addition some H-2, CH4 dissociation as well as destruction channels have been found, among which the CH4 + [Et-O-P(=O)(Me)-S-(CH2)(2)-N+(iPr)=CHMe] product and the destruction product forming Et-O-P(=O)(Me)-SMe + CH2=N+(iPr)(2) are only 9 kcal/mol less stable than the most stable N-protonated product. For fluoridization, the S-P destruction channel to give Et-O-P(=O)(Me)(F) + [S-(CH2)(2)-N-(iPr)(2)](-) is energetically the most favorable, with a fluoride affinity of -Delta E similar to 44 kcal. Various F- ion-molecule complexes are also found, with the one having F- interacting with two hydrogen atoms in different alkyl groups to be only 9 kcal/mol higher than the above destruction product. These results suggest VX behaves quite differently from surrogate systems.
引用
收藏
页码:13189 / 13197
页数:9
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