高等学校化学学报
高等學校化學學報
고등학교화학학보
Chemical Journal of Chinese Universities
2015年
11期
2163-2170
,共8页
溴碘甲烷%光解离%溶剂化效应%完全活化空间二阶微扰%旋轨耦合%从头算
溴碘甲烷%光解離%溶劑化效應%完全活化空間二階微擾%鏇軌耦閤%從頭算
추전갑완%광해리%용제화효응%완전활화공간이계미우%선궤우합%종두산
Bromoiodomethane%Photolysis%Solvent effect%CASPT2%Spin-orbit coupling%ab initio
基于CH2 BrI光解离的最新实验报道，采用多态完全活化空间二阶微扰理论和完全活化空间态相互作用-旋轨耦合作用( MS-CASPT2/CASSI-SO)方法，计算了CH2 BrI在乙腈、2-丁醇和环己烷3种溶剂中，在266 nm的光激发下的旋轨耦合态的势能曲线，指认了实验观测到的解离产物I(2P3/2)和I*(2P1/2)的具体解离途径。为了理解不同溶剂对光产物重新结合成CH2 Br—I和CH2 I—Br的影响，对CH2 BrI在溶剂中光异构化过程的反应机理进行了探讨。
基于CH2 BrI光解離的最新實驗報道，採用多態完全活化空間二階微擾理論和完全活化空間態相互作用-鏇軌耦閤作用( MS-CASPT2/CASSI-SO)方法，計算瞭CH2 BrI在乙腈、2-丁醇和環己烷3種溶劑中，在266 nm的光激髮下的鏇軌耦閤態的勢能麯線，指認瞭實驗觀測到的解離產物I(2P3/2)和I*(2P1/2)的具體解離途徑。為瞭理解不同溶劑對光產物重新結閤成CH2 Br—I和CH2 I—Br的影響，對CH2 BrI在溶劑中光異構化過程的反應機理進行瞭探討。
기우CH2 BrI광해리적최신실험보도，채용다태완전활화공간이계미우이론화완전활화공간태상호작용-선궤우합작용( MS-CASPT2/CASSI-SO)방법，계산료CH2 BrI재을정、2-정순화배기완3충용제중，재266 nm적광격발하적선궤우합태적세능곡선，지인료실험관측도적해리산물I(2P3/2)화I*(2P1/2)적구체해리도경。위료리해불동용제대광산물중신결합성CH2 Br—I화CH2 I—Br적영향，대CH2 BrI재용제중광이구화과정적반응궤리진행료탐토。
Based on the latest experimental results in solvents, the state-of-the-art quantum chemical calcula-tion, i. e. the multi-state second order multiconfigurational perturbation theory in consideration of the spin-orbit coupling interaction through complete active space state interaction( MS-CASPT2/CASSI-SO) was used for investigating the spin-orbital-coupled states potential energy curves( PECs) of bromoiodomethane( CH2 BrI) at 266 nm in solvents( acetonitrile, 2-butanol and cyclohexane) . The calculated PECs leading to the products I ( 2 P3/2 ) and I*( 2 P1/2 ) are consistent with the experimental observations. The mechanisms of the photoisomerization in solvents were studied in order to understand the effects of solvent polarity on the recombi-nation products( CH2 Br—I and CH2 I—Br) . The current calculation assigned the latest experimental observa-tion, and once again evidenced the necessity of involving the spin-orbit coupling effect for heavy atoms like Br and I.
