Potential energy surfaces and potential energy well of reaction NO(3)(-)+Cl(2)-> ClONO(2) plus Cl(-)

作者：Chi Shao Ming; Wang Ning; Ma Li Ying; Fang Fang; Tian Guo Cai; Li Guo Bao; Xu Si Chuan^*

来源：Chemical Journal of Chinese Universities, 2008, 29(6): 1228-1233.

• chlorine nitrate
• potential energy surface
• potential energy well
• potential well compound
• chemical dynamics

The reaction potential surfaces (PESes) for the ion-molecule reaction of NO(3)(-) + Cl(2)-> ClONO(2) + Cl(-) were calculated at the B3LYP/6-311 + G(d) level in the mode of three dimensions. Three original three-dimensional PESes prove that in the reaction there are no transition state and energy barrier, but there exists a potential energy well. The depth of the potential energy well is -55.0 kJ/mol (relative to NO(3)(-) and Cl(2) completely be separated) calculated with CCSD(T)/6-311 + G(d)//B3LYP/6-311 + G(d). At the bottom of the well, there is a compound called Potential Well Compound(PWC), existing stably with the help of the well. The calculated theoretical infrared spectra predict that the PWC would be examined in low temperature infrared spectra. Our work shows that at low temperatures( similar to 180 K) the reaction is dominated by its thermal dynamics. When the temperature going up, the PWC decomposes through reaction of( O(2) NOClCl)(-) -> NO(3)(-) + Cl(2), dominated by its chemical dynamics. Our study indicates that ClONO(2) with Cl(-) cannot produce Cl(2) at low temperatures in the gas-phase reaction.

• 出版日期2008-6-10
• 单位云南大学