UNO CI studies of nonlinear optical properties and excited staes of unstable molecules and clusters

UNO CI 研究不稳定分子和团簇的非线性光学性质和激发状态

• 批准号: 04453002
• 负责人: YAMAGUCHI Kizashi
• 金额: $ 4.67万
• 依托单位: Osaka University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1992
• 资助国家: 日本
• 起止时间: 1992 至 1993
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-04453002/
• 关键词: UNO CI; UNO CASSCF; hyperpolarizabilities; NLA method; Polyenes; UNO‐CI; UNO‐CASSCF; ケイ素化合物; ゲルマニウム化合物

In this research project, our UNO-CI computation method has been incorporated into the Alchemy II program package in order to calculate potential curves, excitation energies, transition probabilities, etc.for unstable molecular systems. The UNO CI method has been applied to depict the potential curves of the linear Hn systems and the dimer of triplet methylene. The UNO CASSCF calculations have also been carried out for these systems. It has been established that the UNO-CI wavefunction is a very good trial for the UNO CASSCF calculation. Thus, the computation scheme without external electromagnetic fields has been established.Next, a new method, numerical Liouville approach (NLA), has been proposed in order to investigate the frequency-dependent nonlinear optical responce of molecules and molecular clusters under the strong laser fields. The numerical stability and computational reliability of the NLA method have been examined in details. The NLA method has also been applied to calculate the hyperpolarizabilities of polyenes. The results are in consistent with the experiments in both the off-resonant and resonant regions.Ab initio MO calculations have been performed for clusters of DNBB in order to elucidate factors which determine its crystal structure. It has been found that the hydrogen bonding interaction is the most important factor to control the crystal structure. It is concluded that the effective use of hydrogen bondings is essential for crystal engineering approach towards molecular-based materials.

在本研究项目中，我们的UNO-CI计算方法已被纳入到Alchemy II程序包中，用于计算不稳定分子体系的势曲线、激发能、跃迁概率等。用UNO - CI方法描述了线性Hn体系和三态亚甲基二聚体的电位曲线。联合国办事处也对这些系统进行了CASSCF计算。结果表明，UNO- ci波函数对UNO CASSCF计算是一个很好的尝试。从而建立了无外加电磁场的计算方案。其次，为了研究强激光场下分子和分子团簇的频率相关非线性光学响应，提出了数值Liouville方法（NLA）。对NLA方法的数值稳定性和计算可靠性进行了详细的检验。NLA方法也被用于计算多烯的超极化率。在非谐振区和谐振区得到的结果与实验结果一致。为了阐明决定其晶体结构的因素，对DNBB簇进行了从头到尾的MO计算。研究发现，氢键相互作用是控制晶体结构的最重要因素。研究结果表明，氢键的有效利用对分子基材料的晶体工程研究至关重要。

项目成果

S.Yamanaka: "EHF theory of chemical reactions IV.UNO CASSCF,UNO CASPT2 and R(U)HF coulped-cluster(CC)wavefunctions" J.Mol.Strucxture(Theochem). (in press).

S.Yamanaka：“化学反应的 EHF 理论 IV.UNO CASSCF、UNO CASPT2 和 R(U)HF 耦合簇 (CC) 波函数”J.Mol.Struxture(Theochem)。

M.Okumura: "A MO-theoretical calculation of the antiferromagnetism in the γ-phase of p-nitrophenyl nitronyl nitroxide." Chem.Phys.Lett. 219(1). 36-44 (1994)

M.Okumura：“对硝基苯基硝基硝基氧的 γ 相反铁磁性的 MO 理论计算。Chem.Phys.Lett。”219(1)。

K.Yamaguchi et al.: "Theoretical study of organic magnetisms in “Computer Aided Innovation of New Materials"" Eds.M.Doyama et al.,Elsevier Science Pub., (1993)

K. Yamaguchi 等人：““新材料计算机辅助创新”中有机磁性的理论研究” Eds. M. Doyama 等人，Elsevier Science Pub.，(1993)

S.Yamanaka, et al.: "Heisenberg Model for Radical Reactions III.Direct exchange coupling between transition metal ion and triplet methylene" J.Mol.Strucxture(Theochem). (in press).

S.Yamanaka 等人：“自由基反应的海森堡模型 III.过渡金属离子和三重态亚甲基之间的直接交换耦合”J.Mol.Struxture(Theochem)。

K.Yamaguchi et al.: "Mo Theoretical Studies of Magnetic Intercations for Clusters of Nitrony1 Nitroxide and Related Species" Chem.Phys.Lett.190. 353-360 (1992)

K.Yamaguchi 等人：“Nitrony1 Nitrox 及相关物质簇磁相互作用的 Mo 理论研究”Chem.Phys.Lett.190。