Effect of Excited-state Substituent Constant on the UV Spectra of 1,4-disubstituted Benzenes

构建激发态取代基参数与1,4-二取代苯的紫外吸收波数之间的模型,成功地关联80个1,4-二取代苯的紫外吸收波数,其方程的相关系数为0.9805,标准偏差仅为672.27 cm^-1．结果表明激发态取代基参数适用于1,4-二取代苯紫外吸收能量的研究．同时提供了研究芳香化合物的紫外吸收光谱的新方法,并有利于深入理解多取代共轭化合物的激发态物理化学性质中的取代基效应     

用相互作用势指数估算单取代烷烃生成焓

基于直链烷烃生成焓的实验值提出16种取代基X(OH、SH、NH₂、Br、Cl、I、NO₂、CN、CHO、COOH、CH₃、CH=CH₂、C≡CH、Ph、COCH₃、COOCH₃)的相互作用势指数IPI(X). 用IPI(X)和极化效应指数建立模型,对单取代烷烃RX(包括含支链的化合物)的生成焓进行估算,所得回归方程有良好的相关性,该模型既考虑了基团R和X的贡献,又考虑了R与X相互作用的贡献. 并采用留一法对其稳定性和预测能力进行验证.     

第V类两态叠加多模叠加态光场的广义非线性等阶N次方Y压缩

本文构造了由多模真空态|{0_j}>_q和多模虚相干态的相反态|{-iZ_j}>_q这两者的线性叠加所组成的第V类两态叠加多模叠加态光场|ψ₅⁽²⁾>_q.利用多模压缩态理论,研究了态|ψ₅⁽²⁾>_q的广义非线性等阶N次方Y压缩特性.结果发现:1)态|ψ₅⁽²⁾>_q是一种典型的多模非经典光场;无论压缩阶数N取奇还是取偶,只要各模的初始相位φ_j(j=1,2,3,…,…,q)和态间的初始相位差(θ_nq^(I)-θ_oq^(o))等满足一定的取值条件,态|ψ₅⁽²⁾>_q总可呈现出周期性变化的、任意奇数阶和任意偶数阶的广义非线性等阶N次方Y压缩效应.2)态|ψ₅⁽²⁾>_q所分别呈现的任意奇数阶和任意偶数阶的等阶N次方Y压缩效应,其压缩条件、压缩特征以及压缩程度和压缩深度等各不相同.3)无论压缩阶数N取奇还是取偶,态|ψ₅⁽²⁾>_q的第一和第二这两个正交分量的等阶N次方Y压缩效应总是呈现出周期性的互补关系.     

ErP5O14非晶玻璃的红外量子剪裁

研究了Er_1.0P₅O₁₄铒非晶玻璃的红外量子剪裁现象. 从吸收谱和激发光谱的计算比较中肯定了Er_1.0P₅O₁₄非晶 玻璃的1537.0 nm红外荧光为多光子量子剪裁荧光. 从Er_1.0P₅O₁₄非晶玻璃的可见和红外荧光发射光谱中发现激发²H_11/2, ⁴G_11/2和⁴G_9/2能级所导致的⁴I_13/2→⁴I_15/2量子剪裁红外荧光很强;基于自发辐射速率、无辐射弛豫速率和能量传递速率等参数的计算,对其量子剪裁机理进行了分析.发现起源于基态的强下转换能量传递{²H_11/2→⁴I_9/2,⁴I_15/2→⁴I_13/2},{⁴G_11/2→⁴I_13/2, ⁴I_15/2→²H_11/2},{⁴G_9/2→⁴F_7/2,⁴I_15/2→⁴I_13/2}和{⁴G_9/2→⁴I_13/2, ⁴I_15/2→²H_11/2}是导致Er_1.0P₅O₁₄非晶玻璃具有强的三光子和四光子量子剪裁红外荧光的原因.研究结果对改善太阳能电池效率有一定意义.     

硼羰基络合物正离子B(CO)3+和B2(CO)4+的红外光解离光谱

利用脉冲激光溅射-超声分子束载带方法制备气相硼羰基络合物正离子. 采用红外光解离光谱研究了B(CO)₃⁺、B(CO)₄⁺ 和B₂(CO)₄⁺的振动光谱. 研究结果表明B(CO)₃⁺具有非常强的B-CO键,无法直接获得其红外光解离光谱. 对B(CO)₄⁺的光解离光谱研究表明该离子是一个B(CO)₃⁺和CO之间弱相互作用络合物. 其中B(CO)₃⁺核具有平面D_3h对称性结构,中心硼具有稳定的8电子组态. B₂(CO)₄⁺具有平面的D_2h对称性结构,其中的B-B键包含一个σ键和半个π键. 自然轨道能量分解分析(EDA-NOCV)表明在B(CO)₃⁺和B₂(CO)₄⁺中的B-CO成键作用中OC→B(σ)要比B→CO(π)反馈作用强.     

第Ⅱ种强度不等的非对称两态叠加多模叠加态光场的偶数阶等阶N次方Y压缩

本文构造了由多模复共轭相干态的相反态|{-Z_j^(a)*}>_q与多模虚共轭相干态的相反态|{-iZ_j^(b)*}>_q这两者的线性叠加所组成的第Ⅱ种强度不等的非对称两态叠加多模叠加态光场|Ψ_Ⅱ^(ab)>_q,利用多模压缩态理论研究了态|Ψ_Ⅱ^(ab)>_q的任意偶数阶等阶N次方Y压缩特性.结果发现:1)在压缩阶数N取偶数,即N=2p的条件下,无论p=2m(m=1,2,3,…,…),还是p=2m+1(m=0,1,2,3,…,…),只要构成态|Ψ_Ⅱ^(ab)>_q的两个不同的量子光场态中各对应模的强度(即平均光子数)和初始相位都不相等,亦即R_j^(a)≠R_j^(b)和φ_j^(a)≠φ_j^(b)(j=1,2,3,…,q),并且 ,则当满足一定的量子化条件(或者在一些闭区间内连续取值)时,态|Ψ_Ⅱ^(ab)>_q总可呈现出周期性变化的、任意偶数阶的等阶N次方Y压缩效应.2)在N=2p且p=2m+1(m=0,1,2,3,…,…)的条件下,若R_j^(a)=R_j^(b)和φ_j^(a)=φ_j^(b)(j=1,2,3,…,q),态|Ψ_Ⅱ^(ab)>_q则可呈现出等阶N次方Y压缩简并现象.     

Ar原子偶宇称3p5(2P1/2)nl''[K'']J(l''=1,3)自电离态激发谱线形研究

The even-parity autoionizing resonance series 3p⁵np''[3/2]_1,2, 3p⁵np''[1/2]₁, and 3p⁵nf''[5/2]₃ of Ar have been investigated exciting from the two metastable states 3p⁵4s[3/2]₂ and 3p⁵4s''[1/2]₀ in the photon energy range of 32500-35600 cm^-1 with an experimental bandwidth of ~0.1 cm^-1. The excitation spectra of the even-parity autoionizing resonance series show typical asymmetric line shapes. New level energies, quantum defects, line profile index and resonance widths, resonance lifetime and reduced widths of the autoionizing resonances are derived by a Fano-type line-shape analysis. The line profile index q and the resonance widths Γ are shown to be approximately proportional to the effective principal quantum number n^*. The line separation of the 3p⁵np'' autoionizing resonances is discussed.     

两种特殊四态叠加多模叠加态光场的等N次幂H压缩

根据线性叠加原理,用多模相干态|{Z_j^*}〉q,|{-Z_j^*}〉q及其复共轭|{Z_j^*}〉q和|{-Z_j^*}〉q组成了两种四态叠加多模叠加态光场|Ψ_oe⁽⁴⁾Ⅵ〉q和|Ψ(4)oeⅦ〉q,利用多模压缩态理论研究了它们的等N次幂H压缩,结果发现:态|Ψ_oe⁽⁴⁾Ⅵ〉q和|Ψ(4)oeⅦ〉q具有完全相同的等N次幂H压缩规律;当压缩幂次N与腔模总数q之积,即qN为偶数时,态|Ψ_oe⁽⁴⁾Ⅵ〉q和|Ψ(4)oeⅦ〉q恒处于等幂次N-H最小测不准态或呈现"半相干态效应";当qN为奇数时,在不同条件下,态|Ψ_oe⁽⁴⁾Ⅵ〉q和|Ψ(4)oeⅦ〉q可以呈现三种不同状态:第一正交分量呈现等N次幂H压缩;第二正交分量呈现等N次幂H压缩; 可呈现"半相干态效应".     

取代基对多取代氮苄叉苯胺化合物分子桥键(CH=N)的~(13)CNMR和~1H NMR的影响（英文）

本文合成了53个多取代的氮苄叉苯胺化合物(XBAY),并测定了它们的核磁共振碳谱和氢谱.包括文献己报导的129个二取代的氮苄叉苯胺化合物分子桥键(CH=N)的碳谱(δ_C(CH=N))和氢谱数据(δ_H(CH=N)),本文研究了共182个取代的XBAY中各取代基对其δ_C(CH=N)和δ_H(CH=N)的影响,分别提出了化合物XB AY分子δ_C (CH=N)和δ_H(CH=N)与取代基参数之间的定量回归方程,该方程可以用来预测取代XB AY的δ_C (CH=N)和δ_H(CH=N)数据,研究结果表明:取代基交叉相互作用项(△(∑σ)~2)对该类化合物的δ_C(CH=N)具有比较大的影响,而对其δ_H(CH=N)的影响基本可以忽略;总体而言,取代基X和Y对化合物XBAY分子δ_C(CH=N)的影响比较均衡,而化合物XBAY分子的δ_H(CH=N)则主要受控于取代基X的影响.     

多模虚共轭相干态与多模真空态的叠加态光场的等阶N次方Y压缩

利用多模压缩态理论,研究了多模虚共轭相干态|{iZ_j^*}〉q与多模真空态|{O_j}〉q的叠加态|{Ψ_p⁽²⁾}〉q的广义非线性等阶N次方Y压缩特性.结果发现态|{Ψ_p⁽²⁾}〉q是一种典型的多模非经典光场,它在一定的条件下,可呈现出周期性变化的、任意奇数阶和任意偶数阶的等阶N次方Y压缩效应,而在另外的条件下,则可呈现出等阶N次方Y相似压缩现象.     

1,1''联萘-2,2''-二胺拉曼和红外光谱的实验和DFT计算研究

实验测量了1，1''-联萘-2，2''-二胺（BINAM）的红外吸收光谱、可见光激发普通拉曼光谱、紫外共振拉曼光谱.用电子密度泛函方法计算了BINAM的基态几何构型、振动频率、普通拉曼和近共振拉曼强度.通过实验和理论计算对比，对所得红外和拉曼提出了详细的指认，并且分析了各振动模式的特征.BINAM的紫外共振拉曼光谱与普通拉曼光谱相比较，发现有若干拉曼谱带出现了选择性共振增强.基于共振拉曼强度分析，讨论了BINAM可能的激发态几何结构的变形.     

Shear response of Fe-bearing MgSiO3 post-perovskite at lower mantle pressures

We investigate the shear response of possible slip systems activated in pure and Fe-bearing MgSiO₃ post-perovskite (PPv) through ab initio generalized stacking fault (GSF) energy calculations. Here we show that the [100](001) slip system has the easiest response to plastic shear among ten possible slip systems investigated. Incorporation of Fe²⁺ decreases the strength of all slip systems but does not change the plastic anisotropy style. Therefore, pure and Fe-bearing MgSiO₃ PPv should demonstrate similar LPO patterns with a strong signature of the [100](001) slip system. An aggregate with this deformation texture is expected to produce a V_SH > V_SV type polarization anisotropy, being consistent with seismological observations.     

单层石墨烯杨氏模量的理论模型

石墨烯力学性能的研究对其在半导体技术中的应用是十分重要的,本文基于半连续体模型并结合石墨烯纳米结构特性,通过对原子的描述构建了石墨烯形变分量和位移分量的新关系,从而给出了单层石墨烯结构形变能,并计算了不同尺寸单层石墨烯的杨氏模量值.通过对不同方向杨氏模量的分析,讨论了单层石墨烯的手性行为.结果表明:随着尺寸的增加,单层石墨烯两个方向的杨氏模量分别趋于0.746 TPa和0.743 TPa,当尺寸相同时,两方向杨氏模量的最大差值不超过0.003 TPa,此结果与文献报道结果相符.在小应变情况下,单层石墨烯薄膜呈各向同性,且薄膜尺寸变化对该特性影响不大.该计算结果对研究石墨烯的其它力学特性提供一定的参考价值.     

Field ionization within the forbidden zone

Mass spectra of helium and neon obtained by field ionization in the presence of hydrogen or another low ionization potential gas contain lines indicating noble gas ions with energies exceeding those of the ordinary field ions by 16 or 13 eV, respectively. These ions originate from the apex-adsorbed state within the forbidden zone following excitation by impinging electrons from free-space ionization of the auxiliary gas.     

Surface crystallography by LEED: II. Matrix formalisms for fast LEED intensity calculations: bare substrate,surface barrier,superstructure

Starting from the generalized Darwin theory of McRae we present several approximations for LEED intensity calculations using matrix formalisms. A layer by layer method is derived, applicable to a general case. We then present a multiple order perturbation method for the clean substrate case. Next, the formulation is extended to include the case of a surface barrier and of an overlayer. Finally, our approximations are discussed in connexion with other perturbation methods.     

Comparison of SERRS and RRS excitation profiles of [Fe(tpy)2]2+ (tpy = 2,2':6',2'‐terpyridine) supported by DFT calculations: effect of the electrostatic bonding to chloride‐modified Ag nanoparticles on its vibrational and electronic structure

Nonresonance (or normal) Raman scattering (NRS), resonance Raman scattering (RRS), surface‐enhanced Raman scattering (SERS), and surface‐enhanced RRS (SERRS) spectra of [Fe(tpy)₂]²⁺ complex dication (tpy = 2,2':6',2''‐terpyridine) are reported. The comparison of RRS/NRS and SERRS/SERS excitation profiles of [Fe(tpy)₂]²⁺ spectral bands in the range of 445–780 nm is supported by density functional theory (DFT) calculations, Raman depolarization measurements, comparison of the solid [Fe(tpy)₂](SO₄)₂ and solution RRS spectra, and characterization of the Ag nanoparticle (NP) hydrosol/[Fe(tpy)₂]²⁺ SERS/SERRS active system by surface plasmon extinction spectrum and transmission electron microscopy image of the fractal aggregates (D = 1.82). By DFT calculations, both the Raman active modes and the electronic states of the complex have been assigned to the symmetry species of the D_2d point group. It has been demonstrated that upon the electrostatic bonding of the complex dication to the chloride‐modified Ag NPs, the geometric and ground state electronic structure of the complex and the identity of the three different metal‐to‐ligand charge transfer (¹MLCT) electronic transitions remain preserved. On the other hand, the effect of ion pairing manifests itself by a slight change in localization of one of the electronic transitions (with max. at 552 nm) as well as by promotion of the Herzberg–Teller activation of E modes resulting from coupling of E and B₂ excited electronic states. Finally, the very low, 1 × 10⁻¹¹ M SERRS spectral detection limit of [Fe(tpy)₂]²⁺ at 532‐nm excitation is attributed to a concerted action of the electromagnetic and molecular resonance mechanism, in conjunction to the electrostatic bonding of the complex dication to the chloride‐modified Ag NP surface. Copyright © 2014 John Wiley & Sons, Ltd.     

不同极性溶液中MEH-PPV链内激子扩散的研究

本文采用飞秒时间分辨瞬态光栅技术研究了MEH-PPV在不同极性溶液中的内激子扩散行为. 采用宽带连续白光同时探测瞬态吸收和瞬态光栅信息. 系统地研究了MEH-PPV的振动失相行为以及单激子弛豫和粒子数弛豫动力学. 结果表明，在极性较大的溶剂中，样品溶液的弛豫扩散过程会加快.     

Theoretical investigation of the backbone···π and π···π stacking interactions in substituted-benzene||3-methyl-2′-deoxyadenosine: a perspective to the DNA repair

The π-stacking effects of substituted benzenes on the N-glycosidic bond strength of 3-methyl-2'-deoxyadenosine (3-MDA) were studied by quantum mechanical calculations. Although all substituents enhance the stacking interactions, enhancement is higher for the electron-donating (ED) substituents. When the overall binding energy is separated into the π···π (ΔE_π···π) and backbone···π (ΔE_bb···π) contributions, the ED and electron-withdrawing (EW) substituents increase those contributions, respectively. Both the ED and EW substituents decrease the distance between the centres of stacked rings, while the EW ones increase the N-glycosidic bond length. The electron charge density calculated at the C--N bond critical point (ρ_C–N) is in linear correlation with the backbone···π interaction, not with the π···π interaction. This study also shows that the charge transfer from X-Ben to 3-MDA is in linear correlation with the ΔE_π···π and the change in the charge on the sugar ring is in better accordance with the backbone···π interaction. The N7 proton affinity (PA_N7), with a key role in the depurination process, is highly affected by the π···π interactions. Thus, both interactions must be considered because of the balance between the backbone···π and π···π contributions in these biomolecular systems.     

Raman spectroscopic study of the uranyl titanate mineral euxenite (Y,Ca,U,Ce,Th) (Nb,Ta,Ti)2O6

Raman spectra of the uranyl titanate mineral euxenite were analysed and related to the mineral structure. A comparison is made with the Raman spectra of uranyl oxyhydroxide hydrates. The observed bands are attributed to the Ti O and (UO₂)²⁺ stretching and bending vibrations, as well as lattice vibrations of rare‐earth ions. The Raman bands of euxenite are in harmony with those of the uranyl oxyhydroxides. The mineral euxenite is metamict as is evidenced by the intensity of the U O stretching and bending modes, which are of lower intensity than expected, and with bands that are significantly broader. Copyright © 2010 John Wiley & Sons, Ltd.