Towards highly accurate ab initio thermochemistry of larger systems: benzene.
Towards highly accurate ab initio thermochemistry of larger systems: benzene.
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迈向大型系统的高精度从头热化学：苯。
DOI：
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发表时间：
2011
影响因子：
4.4
通讯作者：
Mihály Kállay
中科院分区：
文献类型：
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作者：
M. Harding;J. Vázquez;J. Gauss;J. Stanton;Mihály Kállay
采用高精度外推从头算热方法，计算了苯的总雾化能和生成热。本文给出了用三重方法和原子自然轨道(ANO)三重和四重Zeta基组微扰处理得到的全立方和(半)对角四次力场的大规模耦合团簇计算方法，包括1500多个基函数和42个关联电子以及零点能量。研究了热方案的修正性能及其贡献相对于系统大小的标度特性。得到了纯量子化学TAE和相应的守恒误差条5463.0±3.1kJ·m o l(-1)，而相应的95%可信区间为±1.8kJ·m o l(-1)。在101.5 K和298.15 K下，苯的生成热分别为83.9±2.1kJ·m ol(-1)和83.9±2.1kJ·m o l(-1)。
The high accuracy extrapolated ab initio thermochemistry (HEAT) protocol is applied to compute the total atomization energy (TAE) and the heat of formation of benzene. Large-scale coupled-cluster calculations with more than 1500 basis functions and 42 correlated electrons as well as zero-point energies based on full cubic and (semi)diagonal quartic force fields obtained with the coupled-cluster singles and doubles with perturbative treatment of the triples method and atomic natural orbital (ANO) triple- and quadruple-zeta basis sets are presented. The performance of modifications to the HEAT scheme and the scaling properties of its contributions with respect to the system size are investigated. A purely quantum-chemical TAE and associated conservative error bar of 5463.0 ± 3.1 kJ mol(-1) are obtained, while the corresponding 95% confidence interval, based on a statistical analysis of HEAT results for other and related molecules, is ± 1.8 kJ mol(-1). The heat of formation of benzene is determined to be 101.5 ± 2.0 kJ mol(-1) and 83.9 ± 2.1 kJ mol(-1) at 0 K and 298.15 K, respectively.
影响因子：
15
作者：
Wheeler, Steven E.;Houk, Kendall N.;Schleyer, Paul V. R.;Allen, Wesley D.
通讯作者：
Allen, Wesley D.