统计方法校正O3LYP方法计算的生成热

引用本文: 王秀军, 龙汨. 统计方法校正O3LYP方法计算的生成热[J]. 物理化学学报, doi: 10.3866/PKU.WHXB201207172 shu

Citation: WANG Xiu-Jun, LONG Mi. Statistical Correction of Heat of Formation Calculated by the O3LYP Method[J]. Acta Physico-Chimica Sinica, doi: 10.3866/PKU.WHXB201207172 shu

统计方法校正O3LYP方法计算的生成热

王秀军 ,
龙汨

基金项目:
国家自然科学基金(20975040) (20975040)

广东省自然科学基金(10351064101000000)资助项目 (10351064101000000)

摘要:

由于引入各种内在近似, 密度泛函理论存在固有误差. 本文采用O3LYP/6-311+G(3df, 2p)//O3LYP/6-31G(d)计算了220个中小型有机分子的生成热(Δ_fH_calc^Θ), 随后应用神经网络(ANN)和多元线性回归(MLR)方法对Δ_fH_calc^Θ进行校正. 采用计算得到的生成热、零点能、分子中原子总数、氢原子个数、双中心成键电子数、双中心反键电子数、单中心价层孤对电子数、单中心内层电子数作为ANN和MLR的描述符. 以180个分子作为训练集构造ANN或MLR模型, 并对40 个独立测试集分子的Δ_fH_calc^Θ进行了预测. 结果表明: 经过ANN和MLR校正后,训练集分子生成热的理论计算值和实验值间的均方根偏差(RMSD)从24.7 kJ·mol^-1分别降低到11.8、13.0 kJ·mol^-1; 独立测试集分子的RMSD从21.3 kJ·mol^-1分别降低到10.4、12.1 kJ·mol^-1. 因此ANN模型的拟合和预测能力要明显优于MLR模型.

关键词:

English

Statistical Correction of Heat of Formation Calculated by the O3LYP Method

WANG Xiu-Jun ,
LONG Mi

1.
Key Laboratory of Fuel Cell Techology of Guangdong, College of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, P. R. China
Received Date: 09 April 2012
Available Online: 17 October 2012
Fund Project:
国家自然科学基金(20975040)

广东省自然科学基金(10351064101000000)资助项目

Abstract:

The results of density functional theory calculations are known to contain inherent numerical errors caused by various intrinsic approximations. In this paper, O3LYP/6-311+G(3df,2p)//O3LYP/6-31G(d) calculations were used to derive the heats of formation (Δ_fH_calc^Θ) of 220 small to medium-sized organic molecules, followed by the application of artificial neural network (ANN) and multiple linear regression (MLR) analyses to correct the values. The physical descriptors chosen were Δ_fH_calc^Θ and zero point energy as well as the total quantities of atoms, hydrogen atoms, 2-center bonds, 2-center antibonds, 1-center valence lone pairs and 1-center core pairs. The ANN and MLR systems were initially constructed using a 180 training set. The trained ANN and MLR systems were subsequently used to predict values of Δ_fH_calc^Θ for a 40 individual testing set. The results demonstrated that the root mean square (RMS) deviations between the calculated and experimental Δ_fH^Θ values in the training set were reduced from 24.7 to 11.8 and 13.0 kJ·mol^-1 after ANN and MLR corrections, respectively. For the individual testing set, the deviations (RMSD) were reduced from 21.3 to 10.4 and 12.1 kJ·mol^-1, respectively. Based on these results, it can be concluded that ANN exhibits superior fitting and predictive abilities compared with MLR.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

统计方法校正O3LYP方法计算的生成热

English

Statistical Correction of Heat of Formation Calculated by the O3LYP Method

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

统计方法校正O3LYP方法计算的生成热

English

Statistical Correction of Heat of Formation Calculated by the O3LYP Method

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

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