在重金属铜、银和金的团簇中电子相关作用的定量估算

在HF和CCSD(T)水平上研究了重金属碲化物团簇M2Te(M=Cu,Ag,Au)的电子相关作用.结果显示,电子相关作用不改变键长,却减小键角大于20°,说明电子相关作用是作用在重金属原子上的一种切向吸引力.理论分析确定,这个吸引力来自于重金属闭壳层d10-d10之间的van der Waals吸引力.通过拟合电子相关势能函数 ,首次估算了电子相关作用的大小和作用模式.     

含重金属硅化物SiM(M=Au,Ag,Cu)的从头算理论研究

在不同电子相关水平上基于相对论和非相对论赝势,对含重金属硅化物SiM(M=Au,Ag,Cu)的基态几何结构和光谱特性进行了研究,并讨论了电子相关效应和相对论效应的影响.结果表明:重金属硅化物SiM(M=Au,Ag,Cu)的基态电子状态是2Π.电子相关效应缩短了金属硅化物的键长,提高了分离能,谐振频率也增加,使SiM(M=Au,Ag,Cu)的结构变得更加紧凑,基态更加稳定.相对论效应加强了它的强度,使三种硅化物更加稳定.相对论作用的顺序为AuSi>AgSi>CuSi.     

相对论效应和电子相关效应对二聚物(M2Te)2,(M=Au,Ag,Cu)的几何构型和稳定性的修正

使用相对论和非相对论赝势,在HF和MP2理论水平上详细研究了电子相关效应和相对论效应对含重金属铜、银和金的二聚物(M2Te)2,(M=Au,Ag,Cu)的几何构型和稳定性的影响.结果显示,电子相关效应缩短二聚物的金属-金属键长和金属-碲键长、提高振动频率、降低能量,使二聚物的结构变得较为刚性和紧凑;相对论效应加强了它的强度,使二聚物更加稳定.?     

相对论效应和电子相关效应对二聚物(M2Te)2,(M=Au,Ag,Cu)的几何构型和稳定性的修正

使用相对论和非相对论赝势,在HF和MP2理论水平上详细研究了电子相关效应和相对论效应对含重金属铜、银和金的二聚物(M     

电子相关和相对论对M2Te(M=Cu,Ag,Au)的几何结构和稳定性的修正

使用相对论的和非相对论的赝势在HF,MP2,CCSD和CCSD(T)水平上计算了M2Te(M=Cu,Ag,Au)的平衡几何和振动频率.计算的结果表明,这些化合物的基态(单态),弯曲结构是稳定的,线性结构是不稳定的.在MP2水平上研究了电子相关对这些化合物的几何结构的修正.电子相关对键角的修正是非常明显的,对于M=Cu,Ag,Au,角∠M-Te-M分别减少了23.3°,21.8°和21.8°.电子相关对键长的修正是微小的.相对论效应轻微地缩短了Au2Te的键长.比较这三个化合物,Au2Te相对稳定.     

重金属团簇(M2Te)3(M=Au, Ag, Cu)赝势从头算研究

使用相对论和非相对论赝势,在HF和MP2理论水平上研究了重金属混合/掺杂团簇(M2Te)3(M=Au, Ag, Cu) 的几何构型和稳定性.结果显示,团簇存在具有D3h,C2v和C3v对称性的三种稳定异构体,并且各异构体之间能量相差很小.电子相关效应对M-M键长的修正十分显著,而对M-Te键长和Te-M-Te键角的修正非常小.相对论效应使所有键长变短、Te-M-Te键角变大.两种效应都提高振动频率、降低能量,使团簇结构变得更加紧凑,使多聚物趋于更加稳定.     

M2As-和M2Br+(M=Cu,Ag,Au)的赝势从头算研究

使用赝势在HF和MP2水平上计算了M2As-和M2Br+(M=Cu,Ag,Au)的平均几何和振动频率。计算的结果表明,这些化合物呈弯曲结构(C2v)。在MP2水平上研究了电子相关对这些化合物的几何结构的修正,键角减少10°到20°。在MP2,MP3,MP4,CCSD,和CCSD(T)水平上还较详细地研究了电子相关对Au2As-的几何结构的修正。通过对这些化合物稳定性的研究,预言了Au2As-的成键可能性。     

电子相关和相对论对M_2Te(M=Cu,Ag,Au)的几何结构和稳定性的修正

使用相对论的和非相对论的赝势在HF ,MP2 ,CCSD和CCSD(T)水平上计算了M2 Te(M =Cu ,Ag ,Au)的平衡几何和振动频率。计算的结果表明 ,这些化合物的基态 (单态 ) ,弯曲结构是稳定的 ,线性结构是不稳定的。在MP2水平上研究了电子相关对这些化合物的几何结构的修正。电子相关对键角的修正是非常明显的 ,对于M =Cu ,Ag ,Au ,角∠M Te M分别减少了 2 3.3°,2 1.8°和 2 1.8°。电子相关对键长的修正是微小的。相对论效应轻微地缩短了Au2 Te的键长。比较这三个化合物 ,Au2 Te相对稳定。     

重金属钋化物分子MPo(2∏),(M=Cu,Ag,Au)的结构和势能函数

利用相对论小核赝势研究了重金属钋化物分子MPo(X2∏),(M=Cu,Ag,Au).用群论方法结合原子分子反应静力学原理导出了分子的基电子状态和相应的离解极限,并在各种电子相关理论水平上计算了它们的平衡几何和振动频率.在此基础上用Murrell-Sorbie函数形式拟和势能曲线,得到了总的解析势能函数,并计算出了光谱数据和力常数.     

电子相关对Xe10+离子4d8-4d75P跃迁系跃迁概率的影响

应用多组态Dirac-Fock(MCDF)方法,对Xe10 离子进行了理论计算,获得了跃迁波长和概率等数据.通过逐步引入4dn-5p(n=1,2,3)电子相关的相互作用组态,重点研究了电子相关效应对4d8-4d75p跃迁系跃迁概率的影响.结果显示电子相关效应显著,表明了欲得到精确的4d8-4d75p的振子强度(跃迁概率)数据,理论计算中至少要包括到4d2-5p2的电子相关组态的影响.与实验测得的跃迁波长比较发现,理论结果与之有着较好的一致性;同时理论跃迁概率在两种规范下的结果符合得相当精确,显示了计算结果的可靠性.     

Diffusion limited cluster aggregation with irreversible slippery bonds

Irreversible diffusion limited cluster aggregation (DLCA) of hard spheres was simulated using Brownian cluster dynamics. Bound spheres were allowed to move freely within a specified range, but no bond breaking was allowed. The structure and size distribution of the clusters was investigated before gelation. The pair correlation function and the static structure factor of the gels were determined as a function of the volume fraction and time. Slippery bonds led to local densification of the clusters and the gels, with a certain degree of order. At low volume fractions densification of the clusters occurred during their growth, but at higher volume fractions it occurred mainly after gelation. At very low volume fractions, the large-scale structure (fractal dimension), size distribution and growth kinetics of the clusters was found to be close to that known for DLCA with rigid bonds. Restructuring of the gels continued for long times, indicating that aging processes in systems with strong attraction do not necessarily involve bond breaking. The mean-square displacement of particles in the gels was determined. It is shown to be highly heterogeneous and to increase with decreasing volume fraction.     

CO2在中性及带负电Be（n=4, 7, 10, 12, m=0, -1）团簇表面的吸附与解离

运用密度泛函理论,对中性及带负电的BeCO2 (n=4, 7, 10, 12, m=0, -1) 团簇进行了构型优化,稳定性和电子性质分析。结果表明：CO2吸附于Ben和Ben-1团簇表面时,C-O键长均有不同程度的伸长。其中Be4CO2-1,Be12CO2-1中CO2分子的一个C-O键自然断裂(伸长量达到了134%和156%),为典型的解离性吸附。Be团簇表现出了较好的吸附CO2分子的能力,特别是带负电以后,吸附能明显增大(约为3.16eV--5.965eV)。电子性质分析表明,带负电升高了相应团簇的前线轨道能级,使轨道杂化发生在费米能级处附近,从而增强了CO2分子与相应团簇的成键能力。     

Distinguishing the monomer to cluster phase transition in concentrated lysozyme solutions by studying the temperature dependence of the short-time dynamics

Recent combined experiments by small angle neutron scattering (SANS) and neutron spin echo (NSE) have demonstrated that dynamic clusters can form in concentrated lysozyme solutions when the right combination of a short-ranged attraction and a long-ranged electrostatic repulsion exists. In this paper, we investigate the temperature effect on the dynamic cluster formation and try to pinpoint the transition concentration from a monomeric protein phase to a cluster phase. Interestingly, even at a relatively high concentration (10% mass fraction), despite the significant change in the SANS patterns that are associated with the change of the short-ranged attraction among proteins, the normalized short-time self-diffusion coefficient is not affected between 5 and 40?°C. This is interpreted as a lack of cluster formation in this condition. However, at larger concentrations such as 17.5% and 22.5% mass fraction, we show that the average hydrodynamic radius increases significantly and causes a large decrease of the normalized self-diffusion coefficient as a result of cluster formation when the temperature is changed from 25 to 5?°C.     

Precision bond lengths for Rydberg Matter clusters K19 in excitation levels n =4, 5 and 6 from rotational radio-frequency emission spectra

Several long series of up to 40 equally spaced lines are observed in the radio-frequency range 15–90?MHz that are attributed to stimulated emission from the electronically excited condensed matter called Rydberg Matter (RM). These frequencies are more than a factor of 1000 smaller than for most ordinary molecules, and if they did not agree with RM clusters they would indicate extremely large and heavy molecules that are unlikely to exist in the gas phase at room temperature. Theoretical predictions for RM clusters agree within 2% with the observed frequencies. Such clusters are planar, six-fold symmetric oblate rotors. The most prominent series with B?=?0.9292?±?0.0001?MHz (3.067?×?10^?5?cm^?1) agrees accurately with the theoretically predicted B value for the cluster K₁₉ in excitation level n?=?4, thus with a K–K bond length of 2.4074?nm. Two other prominent long series agree accurately with K₁₉ at n?=?5 and 6, with bond lengths of 3.804 and 5.518?nm, respectively. The ratio between the interatomic distance and the electron orbit radius for n?=?4 is found to be 2.8433?±?0.0003, a considerable improvement in precision over the theoretical value of 2.9.     

Tin(n=2~7)团簇结构, 稳定性和电荷分布关系的密度泛函研究

利用密度泛函理论中的B3LYP方法, 选择LANL2DZ基组优化Tin(2~7)团簇得到各团簇的稳定结构,然后对稳定结构的束缚能及自然轨道进行分析. 研究结果表明: Tin(n=2~7)团簇都依带帽的形式在前一个团簇的结构基础上加一个原子变化而来; 通过自然轨道分析发现, 团簇原子的轨道存在sp-d杂化, 有大约一个电子从4s转移到了3d, 原子之间亦存在电子转移, 而且除Ti7外, 团簇键长由最外层4d轨道电子和3d轨道共同决定, 在Ti7中, 团簇键长由3d轨道决定.     

Structure and phase transition of a two—dimensional dusty plasma

The structure and phase transition of a two-dimensional (2D) dusty plasma have been investigated in detail bymolecular dynamics simulation. Pair correlation function, static structure factor, mean square displacement, and bondangle correlation function have been calculated to characterize the structural properties. The variation of internalenergy, shear modulus, particle trajectories and structural properties with temperature has been monitored to studythe phase transition of the 2D dusty plasma system. The simulation results are in favour of a two-step continuoustransition for this kind of plasma.     

Electron-correlation-induced band renormalization and Mott transition in Ca1-xSrxVO3

We present the local density approximate+Gutzwiller results for the electronic structure of Ca_1-xSr_xVO₃. The substitution of Sr²⁺ by Ca²⁺ reduces the bandwidth, as the V—O—V bond angle decreases from 180° for SrVO₃ to about 160° for CaVO₃. However, we find that the bandwidth decrease induced by the V—O—V bond angle decrease is smaller as compared to that induced by electron correlation. In correlated electron systems, such as Ca_1-xSr_xVO₃, the correlation effect of 3d electrons plays a leading role in determining the bandwidth. The electron correlation effect and crystal field splitting collaboratively determine whether the compounds will be in a metal state or in a Mott-insulator phase.