量子化学计算辅助化学教学的探索与实践

量子化学的发展不仅为化学教学提供了形象而生动的教学案例,而且也为化学概念和现象提供了具体可视化的解释。以“科研教学互动”为核心,通过具体的量子化学前沿成果辅助教学应用实例、量子化学计算软件辅助教学等方面阐述了量子化学计算在大学化学教学中的应用前景。这种将量子化学计算与化学教学相结合的教育方式,将对化学课程的发展、化学教学的改革及学生科研创新能力的培养起到推动作用。     

黄曲霉素B1及异构体的前线轨道与拉曼光谱研究

采用B3LYP混合泛函和6-311+g(d, p)基组,利用DFT密度泛函理论优化得到了黄曲霉素Aflatoxin B1(cis)(AFB1(cis))及其反式异构体分子AFB1(trans)的稳定结构, 通过单点能计算和几何结构分析,其顺式结构比反式结构更加稳定;计算了两种分子的Raman光谱,并与AFB1(c)粉末的实验Raman光谱进行比较,吻合较好。把最强的三个峰1 582,3 065和1 626 cm-1指认为顺式结构的特征峰,把1 616,3 065和1 659 cm-1指认为反式结构的特征峰;在优化计算的基础上采用Hirshfeld原子划分方法结合Multiwfn软件分析了前线轨道成分,两种分子的亲电能力明显强于其亲核能力,通过计算C1原子在LUMO轨道中的占据权重分别为21.48%和20.62%,预测出C1原子是这两种顺反异构分子夺走DNA中的电子致癌的最主要位点。结果对该类顺反异构分子的检测、转化以及毒性抑制方面具有一定的理论指导意义。     

Orbital stability of periodic traveling wave solutions to the generalized Long-Short wave equations

This paper investigates the orbital stability of periodic traveling wave solutions to the generalized Long-Short wave equations $\left\{\begin{array}{l}i\varepsilon_{t}+\varepsilon_{xx}=n\varepsilon+\alpha|\varepsilon|^{2}\varepsilon,\\n_{t}=(|\varepsilon|^{2})_{x}, x\in R.\end{array} \right.$ Firstly, we show that there exist a smooth curve of positive traveling wave solutions of dnoidal type with a fixed fundamental period $L$ for the generalized Long-Short wave equations. Then, combining the classical method proposed by Benjamin, Bona et al., and detailed spectral analysis given by using Lame equation and Floquet theory, we show that the dnoidal type periodic wave solution is orbitally stable by perturbations with period $L$. As the modulus of the Jacobian elliptic function $k\rightarrow 1$, we obtain the orbital stability results of solitary wave solution with zero asymptotic value for the generalized Long-Short equations. In particular, as $\alpha=0$, we can also obtain the orbital stability results of periodic wave solutions and solitary wave solutions for the long-short wave resonance equations. The results in the present paper improve and extend the previous stability results of long-shore wave equations and its extension equations.     

Ranking efficient decision making units in data envelopment analysis based on reference frontier share

Data envelopment analysis (DEA) is a powerful technique for performance evaluation of decision making units (DMUs). Ranking efficient DMUs based on a rational analysis is an issue that yet needs further research. The impact of each efficient DMU in evaluation of inefficient DMUs can be considered as additional information to discriminating among efficient DMUs. The concept of reference frontier share is introduced in which the share of each efficient DMU in construction of the reference frontier for evaluating inefficient DMUs is considered. For this purpose a model for measuring the reference frontier share of each efficient DMU associated with each inefficient one is proposed and then a total measure is provided based on which the ranking is made. The new approach has the capability for ranking extreme and non-extreme efficient DMUs. Further, it has no problem in dealing with negative data. These facts are verified by theorems, discussions and numerical examples.     

Structure and property of multiple amino acids assembled on the surface of a CNT

Amino acids were placed with maximal filling on the surface of a CNT via hydrogen bonding and H/π interactions. The interaction structures and properties of assembled complexes were investigated via the density functional tight-binding method. The structural parameters and interaction energies were analyzed to identify the weak interaction strengths. We found that the H/π interactions between amino acids and CNTs play more important roles than the hydrogen bonds between amino acids in stabilizing the complex structures. The effect of CNT chirality and amino acid type were also studied. Furthermore, the HOMOs and LUMOs of the representative complexes were also studied to illustrate the interactions. Our data is helpful in the modification of CNTs by biomolecules.     

Measuring multi-configurational character by orbital entanglement

ABSTRACT

One of the most critical tasks at the very beginning of a quantum chemical investigation is the choice of either a multi- or single-configurational method. Naturally, many proposals exist to define a suitable diagnostic of the multi-configurational character for various types of wave functions in order to assist this crucial decision. Here, we present a new orbital-entanglement-based multi-configurational diagnostic termed Z_s(1). The correspondence of orbital entanglement and static (or non-dynamic) electron correlation permits the definition of such a diagnostic. We chose our diagnostic to meet important requirements such as well-defined limits for pure single-configurational and multi-configurational wave functions. The Z_s(1) diagnostic can be evaluated from a partially converged, but qualitatively correct, and therefore inexpensive density matrix renormalisation group wave function as in our recently presented automated active orbital selection protocol. Its robustness and the fact that it can be evaluated at low cost make this diagnostic a practical tool for routine applications.     

Defining donor and acceptor strength in conjugated copolymers

ABSTRACT

The progress in efficiency of organic photovoltaic devices is largely driven by the development of new donor–acceptor (D–A) copolymers. The number of possible D–A combinations escalates rapidly with the ever-increasing number of donor and acceptor units, and the design process often involves a trial-and-error approach. We here present a computationally efficient methodology for the prediction of optical and electronic properties of D–A copolymers based on density functional theory calculations of donor- and acceptor-only homopolymers. Ten donors and eight acceptors are studied, as well as all of their 80 D–A copolymer combinations, showing absorption energies of 1.3–2.3 eV, and absorption strengths varying by up to a factor of 2.5. Focus lies on exhibited trends in frontier orbital energies, optical band gaps, and absorption intensities, as well as their relation to the molecular structure. Based on the results, we define the concept of donor and acceptor strength, and calculate this quantity for all investigated units. The light-harvesting capabilities of the 80 D–A copolymers were also assessed. This gives a valuable theoretical guideline to the design of D–A copolymers with the potential to reduce the synthesis efforts in the development of new polymers.     

Smallest fullerene-like clusters in two-probe device junctions: first principle study

First principle calculations based on density functional theory are realised to investigate the electron transport of the smallest fullerene-like clusters as two-probe junction devices. The junction devices are constructed by mechanically controlled break junction techniques to ensure the maximum stability of the Be₂₀, B₂₀ and N₂₀ cluster molecular junctions. We investigate the density of states, transmission spectrum, molecular orbitals, current and differential conductance characteristics at discrete bias voltages to gain insight about the various transport phenomena occurring in these nano-junctions. The results show that B₂₀ molecule when stringed to gold electrodes works as an ideal nano-device similar to the pure C₂₀ device and is more symmetric in its characteristic nature. However, in N₂₀ molecular device, the conduction is negligible due to the higher atomic interactions within N₂₀ molecule, despite the fact that it is constructed with penta-valent atoms.     

4-氨基-3,5-二硝基吡唑二聚体分子间相互作用的理论研究

在密度泛函（DFT）B3LYP/6-311++G**水平下,求得4-氨基-3,5-二硝基吡唑（LLM-116）二聚体势能面上的4种全优化几何构型。经基组叠加误差（BSSE）和零点能（ZPE）校正, 求得分子间最大相互作用能为 –29.56 kJ×mol-1。研究表明,其相互作用是放热过程,并随着温度的升高,相互作用减弱;自然键轨道（NBO）分析揭示了相互作用的本质;对优化构型进行振动分析,得其红外光谱,并基于统计热力学求得200.0-800.0 K 温度范围从单分子形成二聚体的热力学性质变化。