共查询到11条相似文献,搜索用时 62 毫秒
1.
A trio of thiolate-protected atomically precise gold nanoclusters, [Au_(23)(S-c-C_6H_(11))_(16)]~–, Au24(SCH_2pH~tBu)_(20)and [Au_(25)(SCH_2CH_2pH)_~(18)]~–, are utilized as catalysts for 4-nitrophenol(4-NP) reduction to 4-aminophenol(4-AP).Despite nearly identical sizes(~1 nm), the three nanoclusters possess distinctly different atomic packing structures and surface ligand binding modes, which contribute to different catalytic performance. The [Au_(23)(Sc-C_6H_(11))_(16)]~–nanocluster shows the highest activity with a kinetic rate constant of 0.0370 s~(-1), which is higher than those of Au24(SCH_2pH~tBu)_(20)(0.0090 s~(-1)) and [Au_(25)(SCH_2CH_2pH)_~(18)]~–(0.0242 s~(-1)). Such a trio of gold nanoclusters indicate that the atomic packing mode and electronic structure play a crucial role in determining their catalytic performance. 相似文献
2.
The evolution of the optical absorption spectrum of bimetallic Ag-Au monolayer-protected clusters (MPC) obtained by progressively doping Ag into the experimentally known structure of Au133(SR)52 was predicted via rigorous time-dependent density-functional theory (TDDFT) calculations. In addition to monometallic Au133(SR)52 and Ag133(SR)52 species, 5 different (Ag-Au)133(SR)52 homotops were considered with varying Ag content and site positioning, and their electronic structure and optical response were analyzed in terms of Projected Density Of States (PDOS), the induced or transition electron density, and Transition Component Maps (TCM) at selected excitation energies. It was found that Ag doping led to the effects rather different from those encountered in bare metal clusters. And it was also observed that Ag doping could produce structured spectral features, especially in the 3–4 eV range but also in the optical region if Ag atoms were located in the sub-staple region, as rationalized by the accompanying electronic analysis. Additionally, Au doping into the staples of Ag-rich MPC also gave rise to a more homogeneous induced electron density. These findings show the great sensitivity of the electronic response of MPC nanoalloy systems to the exact location of the alloying sites. 相似文献
3.
采用密度泛函理论B3LYP/6—311++g^**方法对[NH3(H2O)n]^-(n=2—4)团簇的结构和频率进行研究,从而得到[NH3(H2O)n](n=2—4)团簇的基态结构,得到的结构与SubhaPratihar等的研究一致.同时,文章还研究了水氨团簇的电子束缚方式和偶极矩,结果表明,在n=2时,电子束缚方式为表面束缚,而在n=3,4时,既有表面束缚方式,又有内部束缚方式. 相似文献
4.
用线性Muffin-tin轨道(LMTO)能带计算方法对晶格匹配的超晶格系统(ZnS)n/(Si2)n(110)(n=2~5)进行超原胞自洽计算.在此基础上,用冻结势方法计算了该超晶格系统的价带带阶;用四面体方法计算了该系统的联合态密度.结果表明,该超晶格系统的价带带阶约1.5eV.还讨论了(ZnS)n/(Si2)n(110)超晶格系统的光学性质. 相似文献
5.
本文依据多通道量子亏损理论对Ar原子J=0的高激发态结构进行了理论分析,确定了基本结构参量,得到Lu-Fano图和全部分立态能位、通道混合系数,预言了自电离共振结构。 相似文献
6.
7.
立方相GaN/β-SiC(100)(2×1)混合界面的电子结构 总被引:1,自引:1,他引:0
讨论了含有一个混合层的GaN/ β SiC(10 0 ) (2× 1)重构界面模型 ,在此基础上提出了 (2× 1)混合界面在层轨道表象中的微扰势形式 ,计算了立方相GaN/ β SiC(10 0 )异质结中N/Si界面的电子结构和波矢分辨的层态密度 ,详细讨论了混合界面的原子结构对界面电子结构和层态密度的影响 .结果表明 :混合界面降低了表面态的对称性 ,能量简并消失并产生新的界面态 .层态密度计算结果显示 ,几乎所有界面态都局域在界面附近 ,界面上新形成的化学键使半共振态在界面的一侧高度局域 ,在另一侧为扩展态 相似文献
8.
运用第一性原理中的密度泛函理论理论及平面波赝势法,对斜六方相的BiFeO3的电子结构、态密度及光学性质进行了计算.结果表明,在可见光范围内,当入射光波长处于390~410 nm波段时,吸收效果最好,这与实验上发现光电流最强的入射光波段相一致.此时对应的电子跃迁是从O 2p(向上)态的占据轨道向Fe 3d(向下)态的空轨道跃迁. 相似文献
9.
采用Hartree-Fock(HF)及密度泛函理论(Density Functional Theory,DFT)方法,在LANL2DZ和CEP-31G基组水平上,对配合物CpW(CO)2(μ-CO)(μ-PPh2)Fe(CO)3(1)和CpW(CO)3(μ-PPh2)Fe(CO)4(2)的结构进行了优化,并将采用不同方法和基组的优化结果与X射线衍射实验数据对照。结果表明,用量子化学方法优化含重金属原子的较大配合物体系的结构是方便可行的,而且DFT方法在此类计算中有更高的准确度。为日后进一步深入开展含有过渡金属原子的双金属配合物的理论研究提供了可靠的计算依据。 相似文献
10.
采用基于密度泛函理论的全势能线性缀加平面波方法(FLAPW),在局域自旋密度近似(LSDA:local spin density approximation)和广义梯度近似(GGA:generalized gradient approximation)及LSDA/GGA+U下,系统研究了强关联5f电子体系Pu_2O_3的晶体结构,弹性参数,电子态密度和电荷密度.优化计算结果表明,LSDA+U的晶格参数a0和c/a与实验值吻合最好,同时也在不同的近似下计算了Pu_2O_3的弹性参数.与此同时,LSDA/GGA+U计算的态密度在费米能级处分别出现约1.8和2.2eV能隙,而LSDA/GGA的计算结果在费米能级处并无能隙,所以对Pu_2O_3的Pu-5f加U能使体系从导体转变为绝缘体,这与实验测定Pu_2O_3是绝缘性很好吻合.此外,电荷密度计算结果表明,与LSDA相比,LSDA+U计算的Pu-O间电荷密度增加且有明显的成键特征. 相似文献
11.
采用密度泛函理论方法研究不对称团簇(HFBN3)n (n=1-6)的结构和性质。对于n≥2的团簇,B–Nα键易形成,而B–B和Nα–Nα键不存在。讨论了几何参数随团簇尺寸n的变化规律。通过分析团簇平均结合能和二阶差分值,探讨其相对稳定性,发现团簇(HFBN3)3比其它团簇更稳定。计算IR谱有四个特征区。研究了团簇的热力学性质随温度T以及团簇尺寸n的变化趋势。室温下,由焓变可知单体1形成多聚体(2、3、4、5、6)在热力学上有利。 相似文献