High-level ab initio energy divergences between theoretical optimized and experimental geometries
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 | 2000-08-01 |
| 卷号 | 16页码:718-723 |
| ISSN号 | 1000-6818 |
| 关键词 | optimized geometry high-level ab initio energy |
| DOI | 10.3866/PKU.WHXB20000809 |
| 英文摘要 | High-level ab initio, QCISD(T) / 6-311 + G(3 df, 2p), energy from the least accurate theoretical bond distance was calculated and compared with that from the experimental geometry on each of the thirty four diatomic molecules having a relative error (r(opt.) - r(exp.))/r(exp.) of theoretical bond length greater than 2%. These molecules were chosen from all of the sixty first- and second-row diatomic inorganic species collected in the 77th CRC Handbook of Chemistry and Physics involved in our previous comparison of systematic geometry optimizations. It was found, unexpectedly, that QCISD(T) / 6-311 + G(3 df, 2p) calculations did not result in the lowest energy with the experimental bond distance in a few cases, which implies that QCISD(T) / 6-311 + G(3 df, 2p) method has some deficiencies in the point of view of "high-level ab initio". Most of the QCISD (T) / 6-311 + G(3 df, 2p) energy divergences between the two different geometries were less than 4.2 kJ . mol(-1) with six exceptions with BN, CN, CP, N-2, O-2 and SiN molecules and especially on CN radical, which resulted in an error as large as 15.8 kJ . mol(-1) at the MP2 (full) / 6-311G(2 d, p) geometry. For CN, CP and SiN radicals, the energy errors were also from the poor geometry of MP2 optimizations. It was also found that the larger the basis sets used the poorer the geometries were for these three radicals at MP2 level. For the ground state of BN((3)Pi) radical, the experimental bond length 128. 1 pm maybe in doubt and has to be re-examined. For N-2 and O-2, MP2(full) gradient optimization at the basis sets of valence triple-zeta, 6-311G(d, p), improved the geometries as well as the high-level QCISD(T) energies compared with what at the valence double-zeta, 6-310(d, p), basis sets. |
| WOS关键词 | SET MODEL CHEMISTRY ; QUADRATIC CONFIGURATION-INTERACTION ; DENSITY-FUNCTIONAL GEOMETRIES ; GAUSSIAN-2 THEORY ; MOLECULAR-ENERGIES ; 2ND-ROW COMPOUNDS ; ATOMS ; 1ST-ROW |
| WOS研究方向 | Chemistry |
| 语种 | 英语 |
| 出版者 | PEKING UNIV PRESS |
| WOS记录号 | WOS:000088885300009 |
| 源URL | [http://119.78.100.186/handle/113462/36573]  |
| 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.NW Univ Xian, Inst Modern Phys, Xian 710068, Peoples R China 2.Northwestern Polytech Univ, Dept Chem Engn, Xian 710072, Peoples R China |
| 推荐引用方式 GB/T 7714 | Su, KH,Wei, J,Hu, XL,et al. High-level ab initio energy divergences between theoretical optimized and experimental geometries[J]. ACTA PHYSICO-CHIMICA SINICA,2000,16:718-723. |
| APA | Su, KH.,Wei, J.,Hu, XL.,Yue, H.,Lu, L.,...&Wen, ZY.(2000).High-level ab initio energy divergences between theoretical optimized and experimental geometries.ACTA PHYSICO-CHIMICA SINICA,16,718-723. |
| MLA | Su, KH,et al."High-level ab initio energy divergences between theoretical optimized and experimental geometries".ACTA PHYSICO-CHIMICA SINICA 16(2000):718-723. |
入库方式： OAI收割
来源：近代物理研究所
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