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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Dimethyldioxirane,Carbonyl Oxide,and the Transition State Connecting Them: Electronic Structures,Relative Energies,and Vibrational Frequencies
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Dimethyldioxirane,Carbonyl Oxide,and the Transition State Connecting Them: Electronic Structures,Relative Energies,and Vibrational Frequencies

机译：二甲基二环氧乙烷，碳氧化合物和连接它们的过渡态：电子结构，相对能量和振动频率

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摘要

The electronic structures and vibrational frequencies of dimethyl-substituted carbonyl oxide and its cyclic isomer dimethyldioxirane have been investigated using high-level ab initio quantum mechanical techniques with large basis sets.The equilibrium geometries have been optimized at the self-consistent field (SCF),the single and double excitation configuration interaction (CISD),the coupled cluster with single and double excitation (CCSD),and the CCSD with connected triple excitations [CCSD(T)] levels of theory.The absolute and relative energies of carbonyl oxide,dimethyldioxirane,and the transition state between them have also been computed At the highest level of theory employed in this study, TZP CCSD(T),dimethyldioxirane is predicted to be lower in energy than the carbonyl oxide by 23.2 kcal/mol with the inclusion of zero-point vibrationsl energy (ZPVE) corrections.The energy barrier for the cyclization of carbonyl oxide becomes 19.5 kcal/mol at the same level of theory.Harmonic vibrational freuqencies and infrared (IR) intensities are determined at the DZP SCF and TZP SCF levels of theory for the dimethyl-substituted carbonyl oxide and the transition state,and at correlated levels (CISD and CCSD) with DZP and TZP basis sets for dimethyldioxirane.The experimental vibrational frequencies of dimethyldioxirane are assigned using the present theoretical predictions.It is hoped that the theoretical frequencies for the dimethyl carbonyl oxide isomer will stimulate new experiments.
机译：使用具有大基集的高级从头算量子力学技术研究了二甲基取代的羰基氧化物及其环状异构体二甲基二环氧乙烷的电子结构和振动频率，并在自洽场（SCF）上优化了平衡几何构型，单和双激发构型相互作用（CISD），单和双激发耦合簇（CCSD），以及具有连接的三激发[CCSD（T）]水平的CCSD。碳氧化合物，二甲基二环氧乙烷的绝对和相对能，并且还计算了它们之间的过渡态。在本研究中使用的最高理论水平下，TZP CCSD（T）预测二甲基二环氧乙烷的能量比羰基氧化物低23.2 kcal / mol，包括零。点振动能量（ZPVE）校正。在相同理论水平下，羰基氧化物环化的能垒为19.5 kcal / mol。振动频率和红外（IR）强度是在DZP SCF和TZP SCF理论水平下确定的，即二甲基取代的羰基氧化物和过渡态的水平，并在相关水平（CISD和CCSD）下与DZP和TZP基值确定二甲基二环氧乙烷。根据目前的理论预测确定了二甲基二环氧乙烷的实验振动频率，希望二甲基羰基环氧乙烷异构体的理论振动频率能激发新的实验结果。

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