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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Singlet-Triplet Gap, and the Electronic and Vibrational Spectra of Chlorophenylcarbene: A combined Theoretical and Experimental Study
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Singlet-Triplet Gap, and the Electronic and Vibrational Spectra of Chlorophenylcarbene: A combined Theoretical and Experimental Study

机译：单重三重缝隙和氯苯基碳烯的电子和振动光谱：组合的理论和实验研究

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摘要

Minimum energy structures of singlet and triplet chlorophenylcarbene, a prototypical carbene, were computed. The singlet-triplet energy separation was predicted to be 7.84 and 7.70 kcal/mol at the UCCSD(T)/6-31 + G~* and QCISD(T)/6-31 + G~(**) levels of theory, respectively, after zero-point correction. This is slightly larger than that predicted by the CAS(6,6) (4.5 kcal/mol), local spin density approximation (5.6 kcal/mol), and the BLYP (7.3 kcal/mol) methods with the 6-31G~* basis set reported by Trindle et al. The UV-vis and IR spectra of chlorophenylcarbene were analyzed with the aid of the CASPT2/CASSCF(10,10) and the B3LYP/6-31G~* levels of theory, respectively. THe UV-vis and IR spectra of chlorophenylcarbene were assigned on the basis of these calculations. The ab initio calculations predicted the existence of strong absorption bands in the UV and a weak band in the visible in good agreement with published spectra. The long (750 nm) wavelength band corresponds to electron promotion from the lone pair #sigma# (HOMO) to the #pi#~* (LUMO). On the basis of the calculated harmonic frequencies, we cannot assign the 1244 and 1600 cm~(-1) IR bands observed in an argon matrix to chlorophenyl carbene. The most intense IR band (1225 cm~(-1) corresponds to the symmetric C-C stretch of the carbene and aromatic carbon. The asymmetric and symmetric C-C-Cl stretches are assigned to the bands observed at 847 and 739 cm~(-1), respectively.
机译：计算了单线态和三线态氯苯基卡宾（一种典型的卡宾）的最小能级结构。在UCCSD（T）/ 6-31 + G〜*和QCISD（T）/ 6-31 + G〜（**）的理论水平下，单重态-三重态能量分离预计为7.84和7.70 kcal / mol，经过零点校正。这比使用6-31G〜*的CAS（6,6）（4.5 kcal / mol），局部自旋密度近似（5.6 kcal / mol）和BLYP（7.3 kcal / mol）方法预测的要大一些。 Trindle等人报道的基础集。分别借助CASPT2 / CASSCF（10,10）和B3LYP / 6-31G〜*理论水平分析了氯苯基卡宾的紫外-可见光谱和红外光谱。基于这些计算，确定了氯苯基卡宾的紫外可见光谱和红外光谱。从头算计算预测出在紫外线中存在强吸收带，在可见光中存在弱带，这与已公开的光谱非常吻合。较长的（750 nm）波段对应于从孤对＃sigma＃（HOMO）到＃pi＃〜*（LUMO）的电子促进作用。根据计算出的谐波频率，我们无法将在氩气基质中观察到的1244和1600 cm〜（-1）IR波段分配给氯苯基卡宾。最强的红外波段（1225 cm〜（-1）对应于卡宾和芳族碳的对称CC拉伸，不对称和对称CC-Cl拉伸对应于在847和739 cm〜（-1）观察到的波段， 分别。

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