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

基本信息

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

项目摘要

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.

在该研究项目中，我们的UNO-CI计算方法已被合并到Alchemy II程序包中，以计算不稳定的分子系统的潜在曲线，激发能，过渡概率等。 UNO CI方法已应用于描述线性HN系统和三重甲基二聚体的潜在曲线。这些系统也已经进行了UNO CASSCF计算。已经确定UNO-CI波函数是UNO CASSCF计算的非常好的试验。因此，已经建立了没有外部电磁场的计算方案。已经提出了一种新方法，即数值liouville方法（NLA），以研究在强强激光场下分子和分子簇的频率依赖性非线性光学响应。 NLA方法的数值稳定性和计算可靠性已详细研究。 NLA方法还应用于计算多元的超极化。结果与非谐振区域和谐振区域中的实验一致。为DNBB的簇进行了启动MO计算，以阐明确定其晶体结构的因素。已经发现，氢键相互作用是控制晶体结构的最重要因素。可以得出结论，有效使用氢键对于晶体工程材料的晶体工程方法至关重要。