Photoinduced dissociation reactions of silver fluoride cluster ions

Photoinduced dissociation in the ultraviolet region has been investigated for Ag _nF _n-1 ⁺ cluster ions. Photodissociation spectrum of Ag₂F⁺ in the energy of 3.8–5.6 eV exhibits several sharp bands corresponding to the transition to electronically excited states. In this dissociation, only the Ag₂ ⁺ ion was observed as a fragment ion. Theoretical calculation indicates that the parent Ag₂F⁺ ion has a linear Ag-F-Ag equilibrium geometries in the ground and excited states. Since conformational changes by excitation of bending vibration are necessary for the fragmentation of an F atom, this indicates that production of Ag₂ ⁺ from Ag₂F⁺ is a result of internal conversion and following conformational changes.     

一维粗糙面散射的射线追踪法研究

在考虑遮蔽效应的情况下,应用射线追踪法对一维导体和介质的高斯粗糙面的散射系数进行了研究,并分别计算了考虑一次反射和二次反射的散射系数。同时,利用蒙特卡罗法生成一维高斯粗糙面,计算了考虑一次、二次反射和遮蔽时不同均方根斜率粗糙面的平均散射系数。     

Calculation of geometrical coupling coefficients for the hyperspherical harmonics approach

An elegant and fast method for the calculation of geometrical structure coefficients needed for an expansion of a few-body wavefunction and interaction in hyperspherical harmonics has been proposed. A sum rule for the GSC has also been derived, which is useful for an independent check of the coefficients. The proposed method of computation is many orders of magnitude faster than conventional methods.     

Relative Thermodynamic Stabilities of Isomeric Vinyl Ethers Derived from 2-Acetyland 2-Isobutyryltetrahydrofurans. An Experimental and DFT Study

The relative thermodynamic stabilities of four isomeric vinyl ethers obtained by acid-catalyzed cleavage of MeOH from the dimethyl acetals of both 2-acetyltetrahydrofuran and 2-isobutyryltetrahydrofuran have been determined by chemical equilibration in cyclohexane solution. In addition, the structures and relative energies of many of these compounds have also been studied theoretically by DFT calculations. In each series of compounds, the endocyclic isomers, 5-(1-methoxyethyl)-2,3-dihydrofuran and 5-(1-methoxy-2-methylpropyl)-2,3-dihydrofuran, respectively, show the highest thermodynamic stabilities. This is particularly prominent for the vinyl ethers derived from 2-isobutyryltetrahydrofuran in which the equilibrium mixture consists of 90% of the endocyclic isomer at room temperature. The geometrical (exocyclic) isomers of the latter series of compounds show unexpected relative thermodynamic stabilities, but on the basis of the geometry-optimized structures provided by the DFT calculations, a reasonable explanation can be found.     

13顶点金属碳硼烷结构和非线性光学性质的DFT研究

采用量子化学密度泛函理论(DFT)B3LYP/6-31G(d)方法,对4,1,6-MC2B10H1213顶点金属碳硼烷几何构型进行优化,结合有限场(FF)方法计算了它们的极化率和二阶非线性光学(NLO)系数.结果表明,十个13顶点金属碳硼烷分子中1a～6a的二阶NLO系数与其构型纵向扩张呈现相同的规律.分子的前线分子轨道能级差越小,其二阶NLO系数越大.对于不同自旋态的同种金属碳硼烷分子,其偶极矩值为高自旋态大于相应的低自旋态,极化率和二阶NLO系数与自旋多重度没有一致的对应规律,自旋多重度对NLO性质影响不大.     

(KN3)n(n=1~5)团簇结构与性质的密度泛函理论研究

利用密度泛函理论B3LYP方法, 在6-311G*基组水平上对(KN3)n(n=1~5)团簇各种可能的结构进行了几何结构优化, 预测了各团簇的最稳定结构. 并对最稳定结构的振动特性、成键特性、电荷分布和稳定性性质进行了分析研究. 结果表明, 叠氮化合物中叠氮基以直线型存在, KN3团簇最稳定结构为直线型, (KN3)n(n=2~3)团簇最稳定结构为环形结构, (KN3)n(n=4~5)团簇最稳定结构是由(KN3)2团簇最稳定结构形成的平面和空间结构. N-N 键键长在0.1156~0.1196 nm之间, N-K键键长在0.2357~0.2927 nm之间; 叠氮基中间的N原子显示正电性, 两端的N原子显示负电性, 且与K原子直接作用的N原子负电性更强, 金属K原子与N原子之间形成离子键. (KN3)n(n=1~5)团簇最稳定结构的IR光谱最强振动峰均位于2180~2230 cm-1, 振动模式为叠氮基中N-N键的反对称伸缩振动. 稳定性分析显示, (KN3)3团簇具有相对较高的动力学稳定性.     

高场超导MRI系统铁磁屏蔽的几何优化

磁共振成像（MRI）系统是一种重要的医学影像诊断设备,它根据核磁共振原理对处于静磁场中的人体器官进行成像,具有清晰度高和任意层面成像等优点,在医学检查和诊断方面有着重要的作用,与低场MRI相比,高场MRI系统可提高质子的磁化率,增加图像的信噪比,缩短MRI信号采集时间,从而使脑功能成像的信号变化更为明显;但是较高的背景...     

聚合型硼氢化物(BH3)n(n=1-3)的几何结构与光谱的研究

采用不同方法B3P86,B3LYP,MP2和LSDA,结合Dunning的相关一致基组cc-PVTZ,对聚合型硼氢化物(BH₃)_n(n=1-3)分子的可能几何构型进行优化计算,得出最稳定构型的几何参数、电子结构、振动频率和光谱等性质参数,并给出了最稳定结构的总能量(E_T),结合能(E_BT),平均结合能(E_av),电离势(E_IP),能隙(E_g),费米能级(E_F)等.结果表明:采用密度泛函DFT中的方法B3P86计算的能量最低,结构参数更接近文献值;三种硼氢化物分子基态都为1重态,电子态分别为¹A',¹A和¹A; BH₃分子的最稳定几何构型为平面三角形结构;B₂H₆为对称性乙烯式D_2h立体结构,H-B之间生成氢桥式三中心双电子键;B₃H₉为C_3ν立体结构,也生成氢桥式三中心双电子键,但三个氢桥三中心双电子键彼此隔离.最后分析了三种氢化物的红外和拉曼光谱、平均结合能、电离势、能隙和费米能级等特性,说明(BH₃)_n(n=1-3)三分子中B₂H₆最稳定,H-B桥键键长比端键更长,最强峰红外光谱强度最大. 关键词： 聚合型硼氢化物 几何构型 光谱     

结构参量对左手材料通带位置影响的研究

基于金属短板对和连续金属线(short-slab pair and continuous wires)复合结构,从理论上系统地研究了在THz波段结构参量对左手材料通带位置的影响.数值模拟结果表明,改变金属板宽度或厚度、连续金属线的长度或厚度都会引起左手材料通带位置向较高频段偏移. 关键词： 负折射 左手材料 结构参量 通带     

THE PROBABILISTIC PROPERTIES OF THE NONLINEAR AUTOREGRESSIVE MODEL WITH CONDITIONAL HETEROSKEDASTICITY

1.IntroductionTakeseriesmodelswithconditionalheteroskedasticityarewidelyappliedinmanyareassuchasfinancialeconomicsandeconometrics.Consequently,thereisagrowingthetheoreticalinterestinthesemodels.Inthispaper,weareexclusivelyinterestedinthefollowingnonlinearautoregressivemodelwithconditionalheteroskedasticityat=rk(Xt~1,...Iac~p,01) eth(Xt~1,'IXo~~l02)(1.1)withthefollowingassumptions(i){Et}isasequenceofindependelltideticallydistributedrandomvariableswithacommonalmenteveryWherepositivedenistyi…