立方体AgCl微晶中［Fe(CN)6］4-引入的浅电子陷阱阱深与俘获截面的动力学模拟

为了描述在晶体生长阶段掺入［Fe(CN)₆］^4-的立方体AgCl微晶中 光电子的产生与 衰减过程，建立了一种由三个固有中心和一个浅电子陷阱(SETs)组成的动力学模型，并引出一组微分方程.通过求解微分方程得到与实验结果相符合的光电子衰减曲线及其寿命.调整相 关模拟参数，于常温下得到由［Fe(CN)₆］^4-引入的SETs阱深为0.1 15eV，电子俘获截面为2.136×10^-17cm². 关键词： 光电子 浅电子陷阱 俘获截面 AgCl微晶     

掺有K4Fe(CN)6/K3IrCl6/K4Ru(CN)6的AgClBr微晶的光电子时间分辨谱

微波吸收介电谱检测技术具有很高的时间分辨率 ,可用于固体中电子输运特性的无接触测量 ,是研究晶体中光生载流子寿命及其迁移行为的有效方法。本文利用高时间分辨的微波吸收薄膜介电谱检测装置 ,测量了掺杂K4Fe(CN) 6,K3 IrCl6和K4Ru(CN) 6的AgClBr晶体在 35ps超短脉冲激光曝光后的光电子衰减的时间分辨谱。得到了不同的掺杂剂对AgClBr乳剂的自由光电子和浅俘获光电子的时间特性的影响关系。试验结果表明 ,对于所用的 3种乳剂 ,在掺杂量为 1× 10 -6、掺杂位置为 30 %时 ,掺杂K4Fe(CN) 6的AgClBr乳剂的自由光电子衰减时间相对较短 ,感光度相对较高。利用此方法可进一步研究乳剂光电子时间特性与掺杂剂、颗粒形状、颗粒结构、光谱增感和化学增感剂等参数的依赖关系。     

[Cu~ⅡEDTA]~(2-)与[Fe~Ⅱ(CN)_6]~(4-)反应产物的分子光谱研究

按1:1(摩尔比)混合[Cu EDTA]~(2-)和[Fe(CN)_6]~(4-)溶液(pH=8)时,得到一种深红棕色溶液。测定并讨论了此红棕色溶液的电予光谱和红外光谱,据此确定此溶液中生成了不太稳定的氰桥配合物——[EDTA Cu~Ⅱ—NC—Fe~Ⅱ(CN)_5]~(6-)。     

多价抗衡离子诱导聚甲基丙烯酸N,N-二甲基氨基乙酯(PDMAEMA)刷构象转变的UCST行为

本文应用分子场理论,研究pH、[Fe(CN)_6]~(3-)诱导聚甲基丙烯酸N,N-二甲基氨基乙酯(PDMAEMA)刷的上临界溶解温度(UCST)构象转变与结构特性.理论模型考虑p H和[Fe(CN)_6]~(3-)对PDMAEMA刷体系的静电调控作用.研究发现,在不同[Fe(CN)_6]~(3-)浓度、不同p H条件下,PDMAEMA刷呈现了UCST构象转变行为.由于p H调节PDMAEMA单体质子化,[Fe(CN)_6]~(3-)通过与PDMAEMA带正电荷的单体结合,形成了在PDMAEMA链内以[Fe(CN)_6]~(3-)为中介的带电单体间的静电吸引结合.随着温度升高,[Fe(CN)_6]~(3-)与PDMAEMA带正电荷的单体结合被破坏,[Fe(CN)_6]~(3-)在链内凝聚导致的静电屏蔽效应减弱,PDMAEMA链内带电单体间的静电排斥增强,PDMAEMA刷的构象呈现了从塌缩到溶胀的UCST转变行为,并且在较高[Fe(CN)_6]~(3-)浓度条件下,PDMAEMA刷构象转变的UCST增高.在较低p H值条件下,较多的PDMAEMA单体被质子化,[Fe(CN)_6]~(3-)与PDMAEMA带正电单体的结合增强,PDMAEMA刷构象转变的UCST增大.基于pH和[Fe(CN)_6]~(3-)对PDMAEMA刷体系中的静电调控效应,可以预言,在较小p H和较大[Fe(CN)_6]~(3-)浓度条件下,PDMAEMA链在垂直培基表面沿着链方向形成结节状结构.这是由于以[Fe(CN)_6]~(3-)为中介的链内带电单体间的静电吸引作用增强,导致临近单体间汇聚结节.我们的理论结果符合实验观测,由此表明,pH调节PDMAEMA单体的带电状态,以及[Fe(CN)_6]~(3-)在PDMAEMA链内凝聚导致的静电屏蔽效应,决定着PDMAEMA刷的UCST构象转变和结构特性.     

双金属化合物[Ni(en)2]3[Fe(CN)6]2·2H2O的变温穆斯堡尔谱研究

合成了一维绳梯链状双金属化合物[Ni(en)2]3[Fe(CN)6]2·2H2O,并对其变温穆斯堡尔谱进行了研究,结果表明该分子磁体中铁的电子态为低自旋Fe3 ,而大的四极分裂值(QS)表明此化合物的[Fe(CN)6]3-单元对称结构发生了形变,低温时出现的磁弛豫谱,给出了在该温度点附近出现铁磁耦合相互作用的信息。     

M(Ⅱ)-Fe(Ⅲ)(M=Cu、Co)氰根桥联配合物的穆谱研究

利用穆斯堡尔谱分析合成分子磁体Co[Fe(CN)5NO]·5H2O与[Cu(en)2][KFe(CN)6]·H2O,通过分析超精细相互作用常数来研究其微观结构,研究铁在配合物中价态、价电子排布及同质异能移、四极分裂等超精细相互作用。     

{[K(18-C-6)][K(H2O)2]}[Cd(CN)4]的合成与结构分析

合成了配合物 { [K(18- C- 6 ) ][K(H2 O) 2 ]} [Cd(CN) 4 ](1) ,并通过元素分析、红外光谱、单晶 X-射线衍射进行了结构分析。配合物属单斜晶系 ,空间群 P2 (1) / n。晶体学数据 :a=0 .936 5 3(18) nm,b=1.6 178(3) nm,c=1.74 81(3) nm,β=91.332 (3)°,V=2 .6 479(9) nm3 ,Z=4 ,Dcalcd=1.4 5 3g/ cm3 ,F(0 0 0 ) =12 0 8,R1=0 .0 317,w R2 =0 .0 5 6 7。配合物中 [K(18- C- 6 ) ],[K(H2 O) 2 ]和 [Cd(CN) 4 ]基团通过 K N键和 K —π相互作用形成三维网状结构     

{[K(18-C-6)][K(H_2O)_2]}[Cd(CN)_4]的合成与结构分析

合成了配合物 { [K(18- C- 6 ) ][K(H2 O) 2 ]} [Cd(CN) 4 ](1) ,并通过元素分析、红外光谱、单晶 X-射线衍射进行了结构分析。配合物属单斜晶系 ,空间群 P2 (1) / n。晶体学数据 :a=0 .936 5 3(18) nm,b=1.6 178(3) nm,c=1.74 81(3) nm,β=91.332 (3)°,V=2 .6 479(9) nm3 ,Z=4 ,Dcalcd=1.4 5 3g/ cm3 ,F(0 0 0 ) =12 0 8,R1=0 .0 317,w R2 =0 .0 5 6 7。配合物中 [K(18- C- 6 ) ],[K(H2 O) 2 ]和 [Cd(CN) 4 ]基团通过 K N键和 K —π相互作用形成三维网状结构     

掺杂的AgCl微晶在化学增感条件下的光电子衰减特性

利用微波吸收介电谱技术研究了K₄Fe(CN)₆浅电子陷阱掺杂剂和S+Au增感剂对立方体AgCl微晶光生电子衰减时间分辨特性的影响。结果表明,掺杂浓度为10-8～10-7 mol·mol-1Ag时,在增感之前,掺杂位置越接近表面时,光电子衰减过程会变慢,即衰减时间增加;S+Au增感后的掺杂乳剂中光电子衰减变快,说明了增感中心起深电子陷阱作用,当掺杂位置接近表面90%Ag时,光电子衰减时间突然减小,说明表面掺杂中心和增感中心可能发生了某些反应。     

[Na(15-C-5)]2[Pd(SCN)4]配合物的合成与结构分析

研究了15-冠-5(15-C-5)与Na2[Pd(SCN)4]的反应,得到的配合物[Na(15-C-5)]2[Pd(SCN)4]通过元素分析、红外光谱、单晶X射线衍射进行了结构分析.该配合物为单斜晶系,空间群C2/c,晶体学数据: a=1.3525(6)nm,b=1.3729(6)nm,c=2.0312(9)nm,β=102.985(6)°,V=3.675(3)nm3,Z=4,F(000)=1696,R1=0.0288,wR2=0.0457.结构分析表明,该配合物由两个[Na(15-C-5)]+配阳离子和一个[Pd(SCN)4]2-配阴离子组成,二者通过Na-N相互作用形成二维网状结构.     

First Observation of the nu(17)-nu(4) Difference Bands of Diborane (10)B(2)H(6) and (11)B(2)H(6)

An analysis of the nu(17)-nu(4) difference bands near 800 cm(-1) of two isotopic species, (10)B(2)H(6) and (11)B(2)H(6), of diborane has been carried out using infrared spectra recorded with a resolution of ca. 0.003 cm(-1). In addition, the nu(17) band of (10)B(2)H(6) has been recorded and assigned. Since this band in (11)B(2)H(6) had already been studied (R. L. Sams, T. A. Blake, S. W. Sharpe, J.-M. Flaud, and W. J. Lafferty, J. Mol. Spectrosc. 191, 331-342 (1998)), it was possible to derive precise energy levels and Hamiltonian constants for the 4(1) vibrational states of both isotopic species. Copyright 2000 Academic Press.     

The 2(3)Delta(g) State of (7)Li(2)

Using pulsed perturbation-facilitated optical-optical double resonance (PFOODR) spectroscopy, the 2(3)Delta(g) state of (7)Li(2) (electronic configuration (varsigma(g)2s) (4ddelta(g)), effective principal quantum number n* = 4.101) has been observed and assigned. Molecular constants and a RKR potential energy curve were obtained. The major molecular constants are Copyright 2000 Academic Press.     

Rovibrational Intensities of the (00(0)3) <-- (10(0)0) Dyad Absorption Bands of (12)C(16)O(2)

Absolute line intensities of (12)C(16)O(2) are experimentally measured for the first time for the (00(0)3)(I) <-- (10(0)0)(II) band at 5687.17 cm(-1) and the (00(0)3)(I) <-- (10(0)0)(I) band at 5584.39 cm(-1). The spectra were obtained using a Bomem DA8 Fourier transform spectrometer and a 25-m base-path White cell at NASA-Ames Research Center. The rotationless bandstrengths at a temperature of 296 K and the Herman-Wallis parameters are S(0)(vib) = 6.68(30) x 10(-25) cm(-1)/(molecule/cm(2)); A(1) = 1.4(9) x 10(-4), and A(2) = -1.1(5) x 10(-5) for the (00(0)3)(I) <-- (10(0)0)(II) band and S(0)(vib) = 6.07(22) x 10(-25) cm(-1)/(molecule/cm(2)); A(1) = 5.2(1.5) x 10(-4) and A(2) = -4.0(7) x 10(-5) for the (00(0)3)(I) <-- (10(0)0)(I) band.     

Theoretical Study of the Collision-Induced Double Transition CO(2) (nu(3) = 1) + N(2) (nu(1) = 1) <-- CO(2) (nu(3) = 0) + N(2) (nu(1) = 0) at 296 K

A procedure is presented for the calculation of the double vibrational collision-induced absorption CO(2) (nu(3) = 1) + N(2) (nu(1) = 1) <-- CO(2) (nu(3) = 0) + N(2) (nu(1) = 0) on the basis of quantum lineshapes computed using an isotropic potential and dipole-induced dipole functions. The linestrengths and energies of the vibration-rotation transitions are treated explicitly for N(2), utilizing the HITRAN database for CO(2). The theoretical absorption profile is compared to recent experimental results. By narrowing the width of the individual lines contributing to the overall absorption profile relative to their values determined for N(2)-N(2) collision-induced absorption, excellent agreement between theory and experiment is obtained. Copyright 2000 Academic Press.     

The v(1)+v(3) Bands of the (16)O(17)O(16)O and (16)O(16)O(17)O Isotopomers of Ozone

Using 0.002 cm(-1) resolution Fourier transform absorption spectra of an (17)O enriched ozone sample, an extensive analysis of the v(1)+v(3) bands of the (16)O(17)O(16)O and (16)O(16)O(17)O isotopomers of ozone has been performed for the first time. The experimental rotational levels of the (101) vibrational states were satisfactorily reproduced using a Hamiltonian matrix that takes into account the observed rovibrational resonances. More precisely, for (16)O(17)O(16)O, as for the other C(2v)-type ozone isotopomers, it was necessary to account for the Coriolis type resonances linking the (101) rotational levels with the levels of the (200) and (002) vibrational states and the Darling-Dennison interaction coupling the levels of (200) with those of (002). For the C(s)-type isotopomer, namely (16)O(16)O(17)O, as for (16)O(16)O(18)O and (16)O(18)O(18)O, it proved necessary to also account for an additional DeltaK(a)&equals+/-2 resonance involving the rotational levels from (101) and (002) (J.-M. Flaud and R. Bacis, Spectrochimica Acta Part A 54, 3-16 (1998)). Using a Hamiltonian matrix which takes these resonances explicitly into account, precise vibrational energies and rotational and coupling constants were deduced, leading to the following band centers: v(0)(v(1)+v(3))=2078.3496 cm(-1) for (16)O(17)O(16)O and v(0)(v(1)+v(3))=2098.8631 cm(-1) for (16)O(16)O(17)O. Copyright 2001 Academic Press.     

The Perturbation between the G(1)Pi(g) and 2(1)Delta(g) States of (7)Li(2)

We have observed the rotational levels in the v = 2, 3, 5, 6, 7, and 8 vibrational manifolds of the 2(1)Delta(g) state of (7)Li(2) via the A(1)Sigma(+)(u) intermediate levels by DeltaLambda = 2 transitions. This violation of the DeltaLambda = 0, +/-1 selection rule is due to the interaction with the G(1)Pi(g) state. Band-by-band deperturbations of the G(1)Pi(g) approximately 2(1)Delta(g) (v(Pi), v(Delta)) = (11, 2), (12, 3), (15, 5), (16, 6), (18, 7), and (19, 8) bands have been performed. Deperturbed molecular constants and rotational-electronic interaction parameters are reported here. Copyright 2000 Academic Press.     

The nu(1) and nu(3) Bands of the (17)O(16)O(17)O Isotopomer of Ozone

Using 0.002 cm(-1) resolution Fourier transform absorption spectra of an (17)O-enriched ozone sample, an extensive analysis of the nu(3) band together with a partial identification of the nu(1) band of the (17)O(16)O(17)O isotopomer of ozone has been performed for the first time. As for other C(2v)-type ozone isotopomers [J.-M. Flaud and R. Bacis, Spectrochim. Acta, Part A 54, 3-16 (1998)], the (001) rotational levels are involved in a Coriolis-type resonance with the levels of the (100) vibrational state. The experimental rotational levels of the (001) and (100) vibrational states have been satisfactorily reproduced using a Hamiltonian matrix which takes into account the observed rovibrational resonances. In this way precise vibrational energies and rotational and coupling constants were deduced and the following band centers nu(0)(nu(3)) = 1030.0946 cm(-1) and nu(0)(nu(1)) = 1086.7490 cm(-1) were obtained for the nu(3) and nu(1) bands, respectively. Copyright 2000 Academic Press.     

Multiple magnetic transitions in single crystals of Ce_(12)Fe_(57.5)As_(41) and La_(12)Fe_(57.5)As_(41)

Measurements of magnetic and transport properties were performed on needle-shaped single crystals of Ce_(12)Fe_(57.5)As_(41)and La_(12)Fe_(57.5)As_(41).The availability of a complete set of data enabled a side-by-side comparison between these two rare earth compounds.Both compounds exhibited multiple magnetic orders within 2-300 K and metamagnetic transitions at various fields.Ferromagnetic transitions with Curie temperatures of 100 and 125 K were found for Ce_(12)Fe_(57.5)As_(41)and La_(12)Fe_(57.5)As_(41),respectively,followed by antiferromagnetic type spin reorientations near Curie temperatures.The magnetic properties underwent complex evolution in the magnetic field for both compounds.An antiferromagnetic phase transition at about 60 K and 0.2 T was observed merely for Ce_(12)Fe_(57.5)As_(41).The field-induced magnetic phase transition occurred from antiferromagnetic to ferromagnetic structure.A strong magnetocrystalline anisotropy was evident from magnetization measurements of Ce_(12)Fe_(57.5)As_(41).A temperature-field phase diagram was present for these two rare earth systems.In addition,a logarithmic temperature dependence of electrical resistivity was observed in the two compounds within a large temperature range of 150-300 K,which is rarely found in 3D-based compounds.It may be related to Kondo scattering described by independent localized Fe 3d moments interacting with conduction electrons.     

CO2同位素分子16O12C16O, 16O12C17O, 16O13C17O配分函数研究

本文主要研究了CO2的三种同位素分子16O12C16O , 16O12C17O ,16O13C17O 70 K~6000 K的总内配分函数 (TIPS)。在总内配分函数的计算中, 转动配分函数的计算采用了McDowell的解析式法, 振动配分函数则采用了简谐振动近似(HOA)获得。最后通过将两配分函数乘积近似计算得出TIPS, 并将其70~3000 K的数据和HITRAN04数据进行了比较, 发现所得结果和数据库符合的较好, 且其误差可以近似看成一条直线。并通过对误差的拟合修订了高温区(3000~6000 K)的计算数据, 给出了在高温下的较为准确的TIPS值。