G3(QCI) model chemistry theoretical procedures
文献类型：期刊论文
| 作者 | Su, KH; Wei, J; Hu, XL; Yue, H; Lu, L; Wang, YB; Wen, ZY |
| 刊名 | ACTA PHYSICO-CHIMICA SINICA
 |
| 出版日期 | 2000-11-01 |
| 卷号 | 16页码:1003-1012 |
| 关键词 | model chemistry theoretical procedures G3 (QCI/fu1) G3 (QCI/fu2) G3 (QCI/fu1) //B3PW91 G3 (QCI/fu2) //B3PW91 |
| ISSN号 | 1000-6818 |
| DOI | 10.3866/PKU.WHXB20001109 |
| 英文摘要 | G3(QCI) model chemistry, which eliminates the uncertainties of basis sets and theoretical methods extrapolation approximations, is defined via eq.: E-0[G3(QCI)] = E[QCISD(T, FC)/G3large] + Delta E(full)+ E(SO) + E(ZPE) + E(HLC) where the electronic energy E[QCISD(T, FC)/G3large] is directly calculated at QCISD(T, FC)/G3large level, the core electron correlation energy DeltaE(full) is calculated at MP2/6-31G(d) (denoted as fu1) or MP2/6-311G( d, p) (denoted as fu2) level and the spin-orbit coupling E(SO) for atomic species is from the experiments as what has been done in the G3([2]) theory. Four varieties of G3(QCI) model chemistry theoretical procedure, namely G3(QCI/fu1), G3(QCI/fu2), G3(QCI/fu1)//B3PW91 and G3(QCI/fu2)//B3PW91, are proposed and tested with the G2-1 test set. The E(HLC)'s have been defined and optimized in the same manner as in G3 theory, which are -3.024n(alpha) - 5.397 n(beta) on molecules and -2.085 n(alpha) - 5.636 n(beta) on atomic species for G3(QCI/fu1), -3.085n(alpha)-5.478n(beta) on molecules and -1.885n(alpha) -5.466n(beta) on atomic species for G3 (QCI/fu2), - 2.495n(alpha) - 5.478n(beta) pn molecules and -1.790n(alpha) - 5.584n(beta) on atomic species for G3(QCI/fu1)//B3PW91 and -2.670n(alpha) -5.380n beta on molecules and -1.923n(alpha) -5.465n(beta) on atomic species for G3 (QCI/fu2) //B3PW91. The over-all accuracy is close to that of the G3 or G3//B3LYP([5]) method published in literature. The average absolute deviations on the G2-1 test set for these models are 4.37, 4.39, 4.06 and 4.02 kJ.mol(-1), respectively, compared with 4.27 for G3 and 4.05([32]) for G3//B3LYP on the same G2-1 test set. These results show further that the additivity or extrapolation approximation in the G3 theory is valid. However, the non-additive G3(QCI) procedures, which would be about four times of computer time consuming, in this work has been shown([10]) more reliable in the energy calculation of species at non-equilibrium geometry. The maximum deviation of all of the four G3(QCI)'s occurs on the electronic affinity of the oxygen atom, e.g. -16.7 for G3(QCI/fu1) and -16.9 kJ.mol(-1) for others compared with 17.6 for G3 and 18.4 kJ.mol(-1) for G3//B3LYP on the electronic affinity of NH radical. In addition, this work suggests that the G3large basis sets for the first-row atoms are too small or the level of core-electronic energy calculations for the anions are too low since most of the larger errors are in the respective electronic affinities and this need to be further studied. |
| WOS关键词 | QUADRATIC CONFIGURATION-INTERACTION ; DENSITY-FUNCTIONAL GEOMETRIES ; GAUSSIAN-3 THEORY ; ATOMIZATION ENERGIES ; MOLLER-PLESSET ; COMPUTATION ; FREQUENCIES ; MOLECULES ; ATOMS ; FOCK |
| WOS研究方向 | Chemistry |
| 语种 | 英语 |
| WOS记录号 | WOS:000165669600009 |
| 出版者 | PEKING UNIV PRESS |
| 源URL | [http://119.78.100.186/handle/113462/36333]  |
| 专题 | 中国科学院近代物理研究所 |
| 通讯作者 | Su, KH |
| 作者单位 | 1.Northwestern Polytech Univ, Dept Chem Engn, Xian 710072, Peoples R China 2.NW Univ Xian, Inst Modern Phys, Xian 710068, Peoples R China |
| 推荐引用方式 GB/T 7714 | Su, KH,Wei, J,Hu, XL,et al. G3(QCI) model chemistry theoretical procedures[J]. ACTA PHYSICO-CHIMICA SINICA,2000,16:1003-1012. |
| APA | Su, KH.,Wei, J.,Hu, XL.,Yue, H.,Lu, L.,...&Wen, ZY.(2000).G3(QCI) model chemistry theoretical procedures.ACTA PHYSICO-CHIMICA SINICA,16,1003-1012. |
| MLA | Su, KH,et al."G3(QCI) model chemistry theoretical procedures".ACTA PHYSICO-CHIMICA SINICA 16(2000):1003-1012. |
入库方式： OAI收割
来源：近代物理研究所
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