Wagner J Philipp, Reisenauer Hans Peter, Hirvonen Viivi, Wu Chia-Hua, Tyberg Joseph L, Allen Wesley D, Schreiner Peter R
Institute of Organic Chemistry, Justus-Liebig University, Heinrich-Buff-Ring 17, D-35392 Giessen, Germany.
Center for Computational Quantum Chemistry and Department of Chemistry, University of Georgia, Athens, Georgia 30602, USA.
Chem Commun (Camb). 2016 Jun 14;52(50):7858-61. doi: 10.1039/c6cc01756h.
The cis,trans-conformer of carbonic acid (H2CO3), generated by near-infrared radiation, undergoes an unreported quantum mechanical tunnelling rotamerization with half-lives in cryogenic matrices of 4-20 h, depending on temperature and host material. First-principles quantum chemistry at high levels of theory gives a tunnelling half-life of about 1 h, quite near those measured for the fastest rotamerizations.
由近红外辐射产生的碳酸（H₂CO₃）的顺式、反式构象异构体经历了一种未被报道的量子力学隧穿旋转异构化过程，在低温基质中的半衰期为4 - 20小时，这取决于温度和主体材料。高水平理论下的第一性原理量子化学给出的隧穿半衰期约为1小时，与测量到的最快旋转异构化半衰期非常接近。
