Development of a new molecular orbital theory for avoiding the basis set superposition error in the molecular interaction energy

发展新的分子轨道理论以避免分子相互作用能中的基组叠加误差

• 批准号: 14540479
• 负责人: IWATA Suehiro
• 金额: $ 1.79万
• 依托单位: HIROSHIMA UNIVERSITY (2004)National Institution for Academic Degrees and University Evaluation (2002-2003)
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2004
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-14540479/
• 关键词: Molecular Orbital; Perturbation theory; Molecular interaction; Projection operator; Rare gas clusters; Molecular cluster; 局所射影; クラスター; 一電子物理量; 水クラスター

1)For the clusters consisting of the closed shell molecules, the MP2 level of theory based on the locally-projected molecular orbital theory (LP MO) was developed, and the computer codes were written. A few test calculations showed promising results ; a)the calculated binding energy with the charge-transfer terms is close to the counterpoise corrected SCF binding energy. b)The dispersion-exchange term contributes substantially to the binding energy, particularly near the potential energy minimum.2)The basis set superpose error(BSSE) for the one-electron properties are examined, and are compared with the LP MO MP2(CT). It turns out that the BSSE is less serious than for the binding energy in most of the examples examined.3)Using the projection operators, the stationary condition for closed shell and high-spin open shell molecular orbital coefficients is derived without the orthogonality condition, and a method to solve the equation is proposed. It can be an alternative and direct method to obtain the localized molecular orbitals4)The equations of LP MO for the high-spin open shell cluster, which consists of one open shell molecule and many closed shell molecules, is derived, and the coding is under development.5)With LP MO method and MP2 method, the ionic clusters, M^+(Ar)_n (M=Li,Na,K) were studied. By examining the optimized geometries and the potential energy surfaces, the interaction terms are analyzed.

1)针对由闭合壳层分子组成的团簇，建立了基于局部投影分子轨道理论(LP MO)的MP2水平理论，并编写了相应的计算机程序。一些测试计算显示了有希望的结果：a)用电荷转移项计算的结合能接近平衡校正的SCF结合能。2)考察了单电子性质的基组叠加误差(BSSE)，并与LP MO MP2(CT)进行了比较。3)利用投影算符，在没有正交性条件的情况下，导出了闭壳和高自旋开壳分子轨道系数的稳定条件，并提出了求解该方程的方法。4)推导了由一个开壳层分子和多个闭壳层分子组成的高自旋开壳团簇的LP MO方程，其编码正在编制中。5)用LP MO方法和MP2方法研究了离子团簇M^+(Ar)n(M=Li，Na，K)。通过考察优化后的几何构型和势能面，分析了相互作用项。

项目成果

Osamu Takahashi, Masaki Mitani, Ko Saito, Suehiro Iwata: "Theoretical Studies on the Molecular Dependence of Bond Dissociation after Core Excitations II. : CH_3CO(CH_2)_nCN, n=0-3"J. Computational Chemistry. 24. 1329-1335 (2003)

Osamu Takahashi、Masaki Mitani、Ko Saito、Suehiro Iwata：“核心激发后键解离的分子依赖性的理论研究 II.：CH_3CO(CH_2)_nCN，n=0-3”J。

Theoretical Studies on the Molecular Dependence of Bond Dissociation after Core Excitations II. : CH_3CO(CH_2)_nCN,n=0-3

核心激发后键解离的分子依赖性的理论研究II。

• 发表时间: 2003
• 期刊: J.Computational Chemistry 24
• 作者: Osamu Takahashi;Masaki Mitani;Ko Saito;Suehiro Iwata
• 通讯作者: Suehiro Iwata

Electronic Spectra and Structures of Solvated NH4 Radicals, NH4(NH3)n (n = 1−8)

溶剂化 NH4 自由基 NH4(NH3)n (n = 1−8) 的电子光谱和结构

• 发表时间: 2002
• 作者: S. Nonose;T. Taguchi;Feiwu Chen;S. Iwata;K. Fuke
• 通讯作者: K. Fuke

Takeshi Nagata, Mutsumi Aoyagi, Suehiro Iwata: "Noble gas clusters doped with a metal ion I. Ab initio studies of Na^+Ar_n"J.Phys.Chem.. 108. 683-690 (2004)

Takeshi Nagata、Mutsumi Aoyagi、Suehiro Iwata：“稀有气体团簇掺杂金属离子 I. Na^ Ar_n 的从头算研究”J.Phys.Chem.. 108. 683-690 (2004)

Noble Gas Clusters Doped with a Metal Ion I : Ab Initio Studies of Na+Ar_n

掺杂金属离子的稀有气体团簇I:Na Ar_n的从头算研究

• 发表时间: 2004
• 期刊: J Phys. Chem 108
• 作者: M.Yagi;S.Tanaka;S.Satomi;S.Ryu;K.Okamura;M.Aoyagi;S.Asano;M.Matsuoka;T. Nagata M. Aoyagi S. Iwata
• 通讯作者: T. Nagata M. Aoyagi S. Iwata