W_nC~(0,±)（n=1-6）团簇的密度泛函理论研究
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摘要
团簇是纳米材料结构的基本结构单元之一,纳米材料的性质可以通过改变团簇的尺寸、结构、组成而设计。因此,对团簇基态结构、稳定性和电子特性的理论研究是新材料微观结构设计中的重要课题之一,对于设计具有特定性能的新材料意义重大。本文采用密度泛函理论中的B3LYP方法在LANL2DZ基组水平上对W_nC~(0,±)(n=1-6)团簇进行了研究,其内容及主要结果如下:
(1)首先对W_nC~(0,±)(n=1-6)团簇各种可能的构型进行了全面几何结构优化,得到了W_nC~(0,±)(n=1-6)团簇的基态结构,发现同尺寸中性、阴阳离子团簇的基态结构比较相似,且大多数基态结构的自旋多重度都较低,这与纯Wn团簇具有较低的自旋多重度类似。当W原子数n>3时,稳定构型从平面转变成立体结构,同时掺入的C原子更趋向于表面最稳定。通过平均结合能和能量二阶差分分析表明,C原子的掺入使得Wn团簇的稳定性增强,当n>1时,同尺寸团簇中阳离子团簇稳定性最强,中性团簇最弱。W_3C团簇稳定性最高,可看作W_nC~(0,±)(n=1～6)团簇的结构基元;
(2)在获得W_nC~(0,±)(n=1-6)团簇基态结构的基础上,我们用DFT的杂化密度泛函B3LYP方法对W_nC~(0,±)(n=1-6)团簇基态结构的物理化学性质作了深入分析,通过自然键轨道(NBO)分析了W_nC~(0,±)(n=1-6)团簇的电子分布以及W-C之间的相互作用,并与纯钨团簇的得失电子能力比了比较;在磁性方面,通过电子自旋密度图和前线分子轨道能级图揭示了W_2C~(0,±)和W_4C~(0,±)团簇磁性的主要来源;分析W_nC~(0,±)(n=1-6)团簇的红外振动光谱特征频率的振动模式,并对相关的红移、蓝移现象给出了解释;通过对极化率的分析,展示了团簇对外电场的响应情况。
综上所述,本论文首次对W_nC~(0,±)(n=1-6)团簇的结构及物理化学性质进行了系统的理论研究,可为理解富钨情况下的碳化钨提供理论依据,同时也为寻找新的功能材料具有一定的理论指导意义。
It is known to us that cluster is a basic constitutional unit of nanomaterials whose properties could be designed by controlling the size, geometry structures and compositions. Therefore, it is an important step to study the ground state structures,stablility and electronic properties of cluster for designing micro structures of a new nanomaterial with prescribed properties. In this article, we have applied density functional theory (B3LYP method) to study W_nC~(0,±)(n=1～6)clusters at Lanl2dz level,the results are as follow:
Firstly, The possible equilibrium geometries of W_nC~(0,±)(n=1～6)clusters are optimized ,and the ground state structures obtained. The calculated results show that: The ground state structure of neutral、anionic and cationic are similar at the same size,and most ground state structure have low spins which is similar with pure Wn clusters ; When n>3, the clusters undergo a transition from two-dimensional structure to three-dimensional structure, and the carbon atom remains on the surface of clusters. Through the average binding-energy and second-order difference of energy analysis, the stability of Wn cluster is increased alone with doped carbon atom. Moreover W_3C is the most stable of W_nC~(0,±)(n=1～6)clusters, so that it takes as the basic structure.
After getting the ground state structures of W_nC~(0,±)(n=1-6) clusters, we carefully analysis various properties of them at the B3LYP/LANL2DZ level. For examples, through natural bonding orbital (NBO) analyzed the electronic distribution and interaction mechanism between W atom and C atom; compared the ability of gain and lose electronic with the pure Wn clusters; in magnetic aspects, electronic spin density figures and the energy level of frontier molecular orbital were used to show the main magnetic origin of W_2C~(0,±) and W_4C~(0,±)clusters; analyzed the infrared vibration features and relevant vibration modes , the red-shift and blue-shift were also explained and exhibited the response of external electric field by analyzing polarizability.
Above all, it is the first time to study the physical and chemical properties of the ground state of W_nC~(0,±)(n=1-6) clusters. All of these cluster researches will play an important role in understanding the rich tungsten cases of tungsten carbide and finding new functional materials.
(1)首先对W_nC~(0,±)(n=1-6)团簇各种可能的构型进行了全面几何结构优化,得到了W_nC~(0,±)(n=1-6)团簇的基态结构,发现同尺寸中性、阴阳离子团簇的基态结构比较相似,且大多数基态结构的自旋多重度都较低,这与纯Wn团簇具有较低的自旋多重度类似。当W原子数n>3时,稳定构型从平面转变成立体结构,同时掺入的C原子更趋向于表面最稳定。通过平均结合能和能量二阶差分分析表明,C原子的掺入使得Wn团簇的稳定性增强,当n>1时,同尺寸团簇中阳离子团簇稳定性最强,中性团簇最弱。W_3C团簇稳定性最高,可看作W_nC~(0,±)(n=1～6)团簇的结构基元;
(2)在获得W_nC~(0,±)(n=1-6)团簇基态结构的基础上,我们用DFT的杂化密度泛函B3LYP方法对W_nC~(0,±)(n=1-6)团簇基态结构的物理化学性质作了深入分析,通过自然键轨道(NBO)分析了W_nC~(0,±)(n=1-6)团簇的电子分布以及W-C之间的相互作用,并与纯钨团簇的得失电子能力比了比较;在磁性方面,通过电子自旋密度图和前线分子轨道能级图揭示了W_2C~(0,±)和W_4C~(0,±)团簇磁性的主要来源;分析W_nC~(0,±)(n=1-6)团簇的红外振动光谱特征频率的振动模式,并对相关的红移、蓝移现象给出了解释;通过对极化率的分析,展示了团簇对外电场的响应情况。
综上所述,本论文首次对W_nC~(0,±)(n=1-6)团簇的结构及物理化学性质进行了系统的理论研究,可为理解富钨情况下的碳化钨提供理论依据,同时也为寻找新的功能材料具有一定的理论指导意义。
It is known to us that cluster is a basic constitutional unit of nanomaterials whose properties could be designed by controlling the size, geometry structures and compositions. Therefore, it is an important step to study the ground state structures,stablility and electronic properties of cluster for designing micro structures of a new nanomaterial with prescribed properties. In this article, we have applied density functional theory (B3LYP method) to study W_nC~(0,±)(n=1～6)clusters at Lanl2dz level,the results are as follow:
Firstly, The possible equilibrium geometries of W_nC~(0,±)(n=1～6)clusters are optimized ,and the ground state structures obtained. The calculated results show that: The ground state structure of neutral、anionic and cationic are similar at the same size,and most ground state structure have low spins which is similar with pure Wn clusters ; When n>3, the clusters undergo a transition from two-dimensional structure to three-dimensional structure, and the carbon atom remains on the surface of clusters. Through the average binding-energy and second-order difference of energy analysis, the stability of Wn cluster is increased alone with doped carbon atom. Moreover W_3C is the most stable of W_nC~(0,±)(n=1～6)clusters, so that it takes as the basic structure.
After getting the ground state structures of W_nC~(0,±)(n=1-6) clusters, we carefully analysis various properties of them at the B3LYP/LANL2DZ level. For examples, through natural bonding orbital (NBO) analyzed the electronic distribution and interaction mechanism between W atom and C atom; compared the ability of gain and lose electronic with the pure Wn clusters; in magnetic aspects, electronic spin density figures and the energy level of frontier molecular orbital were used to show the main magnetic origin of W_2C~(0,±) and W_4C~(0,±)clusters; analyzed the infrared vibration features and relevant vibration modes , the red-shift and blue-shift were also explained and exhibited the response of external electric field by analyzing polarizability.
Above all, it is the first time to study the physical and chemical properties of the ground state of W_nC~(0,±)(n=1-6) clusters. All of these cluster researches will play an important role in understanding the rich tungsten cases of tungsten carbide and finding new functional materials.
引文
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[2] H. S. Nalwa. Encyclopedia and Nanotechnology [M]. New York: American Scientific. 2004, 33.
[3]阎守胜.固体物理基础[M].北京:北京大学出版社.2000. 350-351.
[4] L. Hohugven and A. Rosén, Vanadium clusters: Reactivity with CO, NO, O2 and N2 [J]. J. chem.phys. 1999, 110: 2629-2636.
[5] M. P. Jigato, et al. Vibrational frequencies for NO chemisorbed on different sites: DFT calculations on Pd clusters [J]. Surf. Sci. 1997, 380: 83-90.
[6] A. N. Andriotis, M.Menon, and G. Froudakis, Catalytic action of Ni atoms in the formation of carbon nanotubes: A molecular dynamics study [J]. Phys. Rev. Lett. 2000, 85:3193-3196.
[7] S. A. Majetich, Y. Jin. Magnetization Directions of Individual Nanoparticles [J].Science. 1999, 284: 470-473.
[8] R. H. Kodama. J. Magn.Magn.Mater. Magnetic nanoparticles[J].1999, 200: 359-372
[9] Y. Volokitin, et al. Thermodynamic properties of nm-sized Pd and Ni particles [J]. Z. Phys. D.1997, 40:136-139.
[10] I. M. L. Billas, J. A. Becker, et al. Magnetic moments of iron clusters with 25 to 700 atoms and their dependence on temperature [J].Phys. Rev.Lett. 1993, 71: 4067-4070.
[11] D. C. Douglass, J. P. Bucher, L. A. Bloomfield. Magic numbers in the magnetic properties of gadolinium clusters [J]. Phys. Rev. Lett. 1992, 68:1774-1777.
[12] P. Ballone, R. O. Jones. Structure and spin in small iron clusters [J].Chem. Phys.Lett. 1995, 233: 632-638.
[13] B. V. Reddy, S. K. Nayak, S. N. Khanna, et al., Electronic structure and magnetism of Rh_n (n=2-13) clusters [J]. Phys. Rev. B. 1999, 59: 5214-5222.
[14] L. Lian, C.–X, Su, and P. B. Armentrout, Collision-induced dissociation of Ni_n~+ (n=2-18) with Xe: Bond energies, geometrical structures, and dissociation pathways [J]. J. Chem. Phys. 1992, 96: 7542-7554.
[15] A. N. Andriotis, N. Lathiotakis, M. Menon, Magnetic properties of clusters of transition metal atoms [J]. Euro.phys. Lett. 1996, 36:37-41.
[16] Lee G H, Huh S H, et al. Photoelectron spectra of small nanophase W metal cluster anions [J]. Chem. Phys .Lett. 1999, 299:309-314.
[17] S J Oh, S H Huh, H K Kim, J W Park, G H Lee. Structural evolution of W nano clusters with increasing cluster size [J]. J .Chem. Phys.1999, 111: 7402-7404.
[18]林秋宝,李仁全,文玉华,朱梓忠. Wn(n=3—27)原子团簇结构的第一性原理计算[J].物理学报, 2008,57(1): 181-185.
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