Calibration and comparison of the Gaussian-2, complete basis set, and density functional methods for computational thermochemistry

等键反应 热化学 加法函数 标准生成焓 化学 高斯分布 基准集 密度泛函理论 绝对偏差 计算化学 数学 热力学 物理化学 统计 物理 数学分析
作者
George A. Petersson,David K. Malick,William G. Wilson,Joseph W. Ochterski,John A. Montgomery,Michael J. Frisch
出处
期刊:Journal of Chemical Physics [American Institute of Physics]
卷期号:109 (24): 10570-10579 被引量:377
标识
DOI:10.1063/1.477794
摘要

We have reexamined several high-accuracy Gaussian-2, complete basis set and density functional methods for computational thermochemistry (in order of increasing speed): G2, G2(MP2), CBS-Q, G2(MP2,SVP), CBS-q, CBS-4, and B3LYP/6-311+G(3df,2p). We have employed ΔfH2980 for the “extended G2 neutral test set” for this comparison. Several errors in previous studies have been corrected and experimental spin-orbit interactions have been included in all calculated atomic energies. The mean absolute deviations from experiment are 1.43, 1.76, 1.19, 1.64, 2.34, 2.66, and 3.43 kcal/mol, respectively. The maximum deviations from experiment are 10.6, 8.8, 8.1, 9.4, 11.4, 12.9, and 24.1 kcal/mol respectively. The species responsible for these maximum errors are in order: SiF4, SiF4, Cl2C=CCl2, F2C=CF2, ClF3, ClF3, and SiCl4. All seven methods have relatively large errors for bonds to halogens, but these errors are sufficiently systematic to benefit from empirical corrections. After a discussion of ill conditioning in the “bond separation reaction” implementation of isodesmic reactions, we determine “isodesmic bond additivity corrections” (BACs) for several types of bonds by least-squares fits to the heats of formation for 76 organic species with up to ten carbons and a variety of heteroatoms. The mean absolute deviations are reduced from 1.49, 1.93, 1.22, 1.53, 2.28, 3.09, and 3.45 kcal/mol to 0.55, 0.57, 0.77, 0.63, 1.03, 0.98, and 1.16 kcal/mol. The maximum errors are reduced to about 3 kcal/mol for all but the DFT method (4.2 kcal/mol). The BACs are especially useful for larger molecules with many similar bonds. For example, the CBS-Q error for Cl2C=CCl2 is reduced from 8.1 to 3.0 kcal/mol and the CBS-4 errors for benzene and naphthalene are reduced from 10.5 and 17.5 to 2.1 and 1.6 kcal/mol, respectively.
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