Bellili A, Linguerri R, Hochlaf M, Puzzarini C
Laboratoire de Modélisation et Simulation Multi Echelle, Université Paris-Est, MSME UMR 8208 CNRS, 5 boulevard Descartes, 77454 Marne-la-Vallée, France.
Dipartimento di Chimica "Giacomo Ciamician," Università di Bologna, Via F. Selmi 2, I-40126 Bologna, Italy.
J Chem Phys. 2015 Nov 14;143(18):184314. doi: 10.1063/1.4935493.
In an effort to provide an accurate structural and spectroscopic characterization of acetyl cyanide, its two enolic isomers and the corresponding cationic species, state-of-the-art computational methods, and approaches have been employed. The coupled-cluster theory including single and double excitations together with a perturbative treatment of triples has been used as starting point in composite schemes accounting for extrapolation to the complete basis-set limit as well as core-valence correlation effects to determine highly accurate molecular structures, fundamental vibrational frequencies, and rotational parameters. The available experimental data for acetyl cyanide allowed us to assess the reliability of our computations: structural, energetic, and spectroscopic properties have been obtained with an overall accuracy of about, or better than, 0.001 Å, 2 kcal/mol, 1-10 MHz, and 11 cm(-1) for bond distances, adiabatic ionization potentials, rotational constants, and fundamental vibrational frequencies, respectively. We are therefore confident that the highly accurate spectroscopic data provided herein can be useful for guiding future experimental investigations and/or astronomical observations.
为了对乙酰氰及其两种烯醇异构体和相应的阳离子物种进行准确的结构和光谱表征，我们采用了最先进的计算方法和途径。包括单重和双重激发以及三重激发微扰处理的耦合簇理论已被用作复合方案的起点，该方案考虑了外推到完全基组极限以及核对价层的相关效应，以确定高精度的分子结构、基本振动频率和转动参数。乙酰氰的现有实验数据使我们能够评估计算的可靠性：对于键长、绝热电离势、转动常数和基本振动频率，分别以约0.001 Å、2 kcal/mol、1 - 10 MHz和11 cm⁻¹或更高的总体精度获得了结构、能量和光谱性质。因此，我们相信本文提供的高精度光谱数据可用于指导未来的实验研究和/或天文观测。
