聚并苯同系分子稳定性及电子极化率规律的研究

引入外电场微扰的量子化学ＣＮＤＯ／２方法，计算了聚并苯同系分子（Ｃ４ｎ＋２Ｈ２ｎ＋４）的能量和电子极化率，结果表明：全价电子极化率和π电子极化率均随并苯数目的增加而增大，但增率逐渐降低，当ｎ值足够大时，增率趋于一常数；极化率沿分子链增长方向的增率远远大于其它方向；π电子极化率的增率高于全价电子，聚并苯同系分子的稳定性规律为：顺反型相当，二者强于均键长型，分子链每增加一个单元（Ｃ４Ｈ２）体系能量降低     

共轭多烯分子极化率的量子化学研究

用引入外电场微扰的cNDO/2法计算了共轭多烯分子各种异构体的全价电子及π体系的极化率;讨论了影响共轭多烯电子极化率的诸因素及其变化规律,并对比了己三烯2种异构体的电子极化率,解释了它们有关物理化学性质间的差异。     

H(HC=N-M)_nH体系的结构及非线性光学性质的理论研究

本文在MP2/6-311+G(d,p)水平下研究了H(HC=N-M)_nH(M=Na,K)(n=1~4)体系的几何构型及非线性光学性质(NLO)。结果显示:碱金属原子n值相同时,体系的极化率(α_0)值及其第一超极化率(β_0)值由Li到K随着碱金属半径的增大而逐渐增大。并随着n值的增加,偶极矩(μ_0)值逐渐减小,α_0值先减小再逐渐增大,β_0值是的呈阶梯式变大的。上述体系均具有较大的β_0值,其中H(HC=N-K)_2H体系的β_0(110810a.u.)值是最大的。是已知体系的H(HC=N-Li)_2H(2179 a.u.)的51倍。说明K原子掺杂是用来提高NLO响应的一种新途径。     

统计学在理化检验中的应用第九讲某些基本的统计假设检验(续)

2　对标准偏差的一致性检验2 .1　 F检验设有两个正态总体 N( μ,σ1 ) ,N( μ,σ2 ) ,要求检验 σ21 和 σ22 是否一致。从两个总体中分别取一个样本 ,样本的容量和标准偏差分别为 n1 、S1 和 n2 、S2 。作统计量 F:F =S21 S22( 5)　　当 σ21 =σ22 成立时 ,F服从自由度为 ( n1 - 1 ,n2 -1 )的 F分布 ,对于给定的显著性水平 α,可以求得两个临界值 f1α和 f2α,使得P{F≤ f1α}=α2 ( 6)P{F≥ f2α}=α2 ( 7)　　当按式 ( 5)算得的 F值满足 :f1α 相似文献   

对屏蔽常数物理本质的讨论

一、引言根据量子力学中心力场模型,多电子原子中某单电子i的近似原子轨道Ψ对应能级ε可表示为ε=-13.6×(Z-S_i)~2/n~(*2)=-13.6(Z~*/n~*)~2 (1)同时引入屏蔽效应和屏蔽常数、有效核电荷、有效主量子数等概念。Slater于1930年,提出一套判定n~*、σ(S_i=∑σ)大小的规则,曾得到广泛应用。之后,许多人从不同角度讨论它、通过不同途径修正它。迄今仅确定σ值大小的规则,即不下十余种。概括起来可分为两类:第一类以Slater、徐光宪为代     

甲基丙烯酸三丁基锡酯与甲基丙烯酸甲酯共聚物的

研究了不同投料比的甲基丙烯酸三丁基锡酯(TBTMA)与甲基丙烯酸甲酯(MMA)共聚物的合成和分级方法,测定了各级分的分子量和对应的特性粘数,订定了Mark-Houwink方程式的K、α值.当n(TBTMA)∶n(MMA)=1∶1时,K=0.225,α=0.46,d=2.32.当n(TBTMA)∶n(MMA)=1∶2时,K=1.69×10-4,α=1.18,d=1.23.     

多烯链平均π电子离域能的递变函数研究

离域能或共振能ED是一个共轭多烯体系中π电子能Eπ与相应数目n个孤立乙烯双键中π电子能总和nEπ之差量[1],即ED=Eπ-nEπ(c=c),由于离域能随双键数目增加而逐渐增大,大小不同的多烯链化合物总离域能不便比较.蒋明谦曾提出了著名的有机结构型性能的同系线性规律,他用多烯链每一个碳碳键上的平均离域能(或每个碳碳双键上的平均离域能)对同系因子(1/α)2/n作图,发现二者均具有良好的直线关系,如H(CH=CH)nH系列,碳碳双键上的平均离域能与同系因子成线性关系,相关系数为0.994,H(CH=CH)nC+H2系列,碳碳键上的平均离域能与同系因子线性相关,相关系数亦为0.994[2].但对于不同系列而言,碳碳键上的离域能和碳碳双键上的离域能不便比较.     

STRUCTURE OF NEODYMIUM TRINITRATE WITH DIPHENYL SULFOXIDE LIGANDS, Nd(N0_3)_3·[(C_6H_5SO]_4

<正> Mr=2278, triclinic, Pl, a=11.154(1), b=14.310(2), c=17.295(2) A, α=84.09(1)°, β=72.97(1)°, r=69:37(1)°, V=2470.2(5)A3, Z=2; 2(MoKα)=12.9cm-1 F(000)=1154, Dx=1.53 g/cm3, room temperature. The final R=0.039, Rw=0.039 with wt=1, S=2.57 for 5710 independent reflections with | Fα|≥2.5σ(F0). The molecular configuration of the Nd-complex is similar to those of the Sm-complex and Pr-complex except for the difference in distances between central metal and the coordinated oxygen atoms.     

TTF+1-π共轭桥-6-氧四联氮阳离子双自由基NLO性质的理论研究

采用量子化学UPBE1PBE结合有限场(FF)方法,对系列TTF+?-π共轭桥-6-氧四联氮阳离子双自由基体系的稳定性,极化率αs和第一超极化率βtot进行研究.结果表明,TTF+?-6-氧四联氮阳离子双自由基引入共轭桥后,随体系共轭性增强,αs和βtot值均增大(体系2S的βtot值除外).自旋多重度和构象对双自由基体系的极化率和第一超极化率都有影响,双自由基体系由单重态转变为三重态时,极化率减小,而第一超极化率明显增大.以体系2为例,在单重态时αs和βtot值随构象变化较小,而三重态时αs和βtot值随二面角θ1和θ2的增加而减小.     

菁染料溶剂效应的光谱研究

本文研究了16种菁染料在18种溶剂中的吸收光谱与激光荧光发射光谱的溶剂效应。发现吸收峰的位移⊿σ_A以及吸收峰与荧光发射峰的能量差(σ_A-ν_F)不仅与溶剂的折射率有关, 而且与其介电常数有关。因而用新函数f(n, e)=((n~2-1)/(2n~2+1))+α((e-1)/(e+2))与F(n, e)=((e-1)/(2e+1))-((n~2-1)/(2n~2+1))代替Bayliss函数f(n)=((n~2-1)/(2n~2+1))可改善结果的线性。还观察到溶剂伋性对染料分子荧光峰位置与强度以及对~1(n, π)及~1(π, π°)能级顺序的影响, 并进行了讨论。     

Depolarization ratio of Rayleigh scattered radiation by molecules

The depolarization ratios of Rayleigh scattered radiation by molecules has been used to measure the ratio of anisotropic polarizability to isotropic (average) polarizability in the laboratory. The authors have calculated the depolarization ratio for N2, CH3Cl, and H2O from the first principles. It is shown that the depolarization ratio derived from input polarizabilities differs by a factor of about 4 for 1Sigma diatom N2, by a factor of about 2.9 for symmetric top CH3Cl, and by a factor of about 5 for asymmetric top H2O. These large discrepancies arise because in deriving the ratio of anisotropic polarizability to isotropic (average) polarizability from the measured depolarization ratio, the constraints imposed by the conservation of angular momentum have been completely ignored.     

分子拓扑学方法估算多环芳香烃类化合物的电离能

It was found that the ionization potentials (Ip) is related with the polarizability effect index (PEI) for the fragments CH, CH2, and CH3 of polycyclic aromatic hydrocarbon. Therefore a kind of adjacent matrix of molecular graph was constructed, in which the characteristics of the diagonal elements were expressed with the PEI of the fragments C, CH, CH2, and CH3 in molecular graph. The research result shows that there is a good correlation between the eigenvalue of the matrix and the ionization potential for the title compounds: Ipi=4.756+2.870OMOi, R=0.9853, s=0.1765, n=446. This new calculation method has only one parameter for calculating ionization potentials of polycyclic aromatic hydrocarbon. The obtained result shows that the topologic molecular method is convenient and reliable.     

The molar polarization and refraction of substances

An equation for the molar polarization of substances that allows electron polarizability of molecules in various states of aggregation (gaseous, liquid, and solid) to be determined is obtained. The Lorenz-Lorentz equation in the traditional form is shown to be inapplicable in principle to calculations of the electron polarizability of molecules in dense media.     

Solvent structural relaxation dynamics in dipolar solvation studied by resonant pump polarizability response spectroscopy

Resonant pump polarizability response spectroscopy (RP-PORS) was used to study the isotropic and anisotropic solvent structural relaxation in solvation. RP-PORS is the optical heterodyne detected transient grating (OHD-TG) spectroscopy with an additional resonant pump pulse. A resonant pump excites the solute-solvent system and the subsequent relaxation of the solute-solvent system is monitored by the OHD-TG spectroscopy. This experimental method allows measuring the dispersive and absorptive parts of the signal as well as fully controlling the beam polarizations of incident pulses and signal. The experimental details of RP-PORS were described. By performing RP-PORS with Coumarin 153(C153) in CH(3)CN and CHCl(3), we have successfully measured the isotropic and anisotropic solvation polarizability spectra following electronic excitation of C153. The isotropic solvation polarizability responses result from the isotropic solvent structural relaxation of the solvent around the solute whereas the anisotropic solvation polarizability responses come from the anisotropic translational relaxation and orientational relaxation. The solvation polarizability responses were found to be solvent-specific. The intramolecular vibrations of CHCl(3) were also found to be coupled to the electronic excitation of C153.     

Static dipole polarizability and binding energy of sodium clusters Nan (n=1-10): A critical assessment of all-electron based post Hartree-Fock and density functional methods

A systematic all electron post Hartree-Fock as well as density functional theory (DFT) based calculations for the polarizability and binding energy of sodium metal clusters have been performed and an in-depth analysis of the discrepancy between the experimental and theoretical results is presented. A systematic investigation for the assessment of different DFT exchange-correlation functionals in predicting the polarizability values has also been reported. All the pure DFT functionals have been found to considerably underestimate the calculated polarizability values as compared to the MP2 results. DFT calculations using the full Hartree-Fock exchange along with one-parameter progressive correlation functional have, however, been shown to yield results in good agreement with the MP2 and experimental results. The possible sources of error present in the experimental measurements as well as in the different theoretical methods have also been analyzed. One of the most important conclusions of the present study is that the effect of electron correlation plays a significant role in determining the polarizability of the clusters and the MP2 method can be considered to be one of the most reliable methods for their prediction. It has also been noted that the polarizability value of the lower member clusters (Na2 and Na4) calculated by highly sophisticated methods such as, CCSD and CCSD(T) are found to be very close to the corresponding MP2 values. The polarizability and the binding energy of the clusters are found to be inversely related to each other and their correlation is rationalized by invoking the minimum polarizability principle. A good linear correlation between the polarizability and volume of the cluster has also been found to exist.     

Quantitative structure-property relationships for longitudinal, transverse, and molecular static polarizabilities in polyynes

The present work reports for the first time quantitative structure-property relationships, derived at the benchmark CCSD(T)/cc-PVTZ level of theory that estimate the static longitudinal, transverse, and molecular polarizability in polyynes (C2nH2), as a function of their length (L). In the case of independent electron models, regardless of the form of the nuclei potential that the electrons experience, the polarizability increases strongly with system size, scaling as L(4). In contrast, the static longitudinal polarizability in polyynes have a considerably weaker length-dependence (L(1.64)). This is shown to predominantly arise from electron-electron repulsion rather than electron correlation by a systematic study of the polarizability length dependence in several simple quantum mechanical systems (e.g., particle-in-box, simple harmonic oscillator) and other molecular systems (e.g., H2, H2(+), polyynes). Decrease of the electron-electron repulsion term is suggested to be the key factor in enhancing nonlinear polarizability characteristics of linear oligomeric and polymeric materials.     

Microsolvation of Co2+ and Ni2+ by acetonitrile and water: photodissociation dynamics of M(2+)(CH3CN)n(H2O)m

The microsolvation of cobalt and nickel dications by acetonitrile and water is studied by measuring photofragment spectra at 355, 532 and 560-660 nm. Ions are produced by electrospray, thermalized in an ion trap and mass selected by time of flight. The photodissociation yield, products and their branching ratios depend on the metal, cluster size and composition. Proton transfer is only observed in water-containing clusters and is enhanced with increasing water content. Also, nickel-containing clusters are more likely to undergo charge reduction than those with cobalt. The homogeneous clusters with acetonitrile M(2+)(CH(3)CN)(n) (n = 3 and 4) dissociate by simple solvent loss; n = 2 clusters dissociate by electron transfer. Mixed acetonitrile/water clusters display more interesting dissociation dynamics. Again, larger clusters (n = 3 and 4) show simple solvent loss. Water loss is substantially favored over acetonitrile loss, which is understandable because acetonitrile is a stronger ligand due to its higher dipole moment and polarizability. Proton transfer, forming H(+)(CH(3)CN), is observed as a minor channel for M(2+)(CH(3)CN)(2)(H(2)O)(2) and M(2+)(CH(3)CN)(2)(H(2)O) but is not seen in M(2+)(CH(3)CN)(3)(H(2)O). Studies of deuterated clusters confirm that water acts as the proton donor. We previously observed proton loss as the major channel for photolysis of M(2+)(H(2)O)(4). Measurements of the photodissociation yield reveal that four-coordinate Co(2+) clusters dissociate more readily than Ni(2+) clusters whereas for the three-coordinate clusters, dissociation is more efficient for Ni(2+) clusters. For the two-coordinate clusters, dissociation is via electron transfer and the yield is low for both metals. Calculations of reaction energetics, dissociation barriers, and the positions of excited electronic states complement the experimental work. Proton transfer in photolysis of Co(2+)(CH(3)CN)(2)(H(2)O) is calculated to occur via a (CH(3)CN)Co(2+)-OH(-)-H(+)(NCCH(3)) salt-bridge transition state, reducing kinetic energy release in the dissociation.     

Polarizability as a local functional of the electron density

Expressions for the multipole polarizability and shielding factor for an atom are obtained using the model where the total electron energy is assumed to be a local functional of the electron density. This simple model correctly predicts the leading term in the 1/Z expansion of the polarizability. Further, the simple local density functional for the polarizability, when evaluated with ground-state Hartree-Fock densities, yields numerical values for atoms which are, in general, in reasonable agreement with those obtained from coupled Hartree-Fock theory.