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1.
The x-ray diffraction intensities of Bragg reflections have been measured at room temperature for thulium selenide, samarium sulphide, samarium selenide and samarium telluride. On the basis of a common amplitude approximation, the Debye-Waller factor, the mean amplitude of vibration and the Debye temperature have been evaluated. The values of the Debye temperatures and mean amplitudes of vibration are 176±16°K, 0·185 ± 0·017 Å (TmSe), 155 ± 7°K, 0·244 ± 0·012 Å (SmS), 153 ± 14°K, 0·221 ± 0·020 Å (SmSe) and 151 ± 20°K, 0·204 ± 0·027 Å (SmTe). 相似文献
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Dance ZE Ahrens MJ Vega AM Ricks AB McCamant DW Ratner MA Wasielewski MR 《Journal of the American Chemical Society》2008,130(3):830-832
Understanding how the electronic structures of electron donor-bridge-acceptor (D-B-A) molecules influence the lifetimes of radical ion pairs (RPs) photogenerated within them (D+*-B-A-*) is critical to designing and developing molecular systems for solar energy conversion. A general question that often arises is whether the HOMOs or LUMOs of D, B, and A within D+*-B-A-* are primarily involved in charge recombination. We have developed a new series of D-B-A molecules consisting of a 3,5-dimethyl-4-(9-anthracenyl)julolidine (DMJ-An) electron donor linked to a naphthalene-1,8:4,5-bis(dicarboximide) (NI) acceptor via a series of Phn oligomers, where n = 1-4, to give DMJ-An-Phn-NI. The photoexcited charge transfer state of DMJ-An acts as a high-potential photoreductant to rapidly and nearly quantitatively transfer an electron across the Phn bridge to produce a spin-coherent singlet RP 1(DMJ+*-An-Phn-NI-*). Subsequent radical pair intersystem crossing yields 3(DMJ+*-An-Phn-NI-*). Charge recombination within the triplet RP then gives the neutral triplet state. Time-resolved EPR spectroscopy shows directly that charge recombination of the RP initially produces a spin-polarized triplet state, DMJ-An-Phn-3*NI, that can only be produced by hole transfer involving the HOMOs of D, B, and A within the D-B-A system. After the initial formation of DMJ-An-Phn-3*NI, triplet-triplet energy transfer occurs to produce DMJ-3*An-Phn-NI with rate constants that show a distance dependence consistent with those determined for charge separation and recombination. 相似文献
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位于藏东南的帕隆藏布流域,处在东喜马拉雅构造结的北缘,是新构造强烈隆升区,断层、褶皱等地质构造发育。在青藏高原隆升及气候变化等内外动力作用下,研究区内堆积体分布广泛,具有独特的工程地质特征并成为该区内地质灾害的主要物源。由于河流的下切及川藏公路的修建,形成了许多高陡的堆积体边坡,以冰碛边坡最为典型。由于其特殊的物源特征及形成过程,冰碛物具有粒度分布范围广、粗粒含量多等与其他沉积物不同的粒度特征。冰碛物粒度分布范围广的特征,导致随着研究尺度的不同,其结构特征也不相同,具有明显的尺度效应。冰碛土的力学强度一般强于其他堆积体,但受不同粒径颗粒的含量及分布、形成时代的影响,其力学特征也有所差异。作者对川藏公路沿线部分典型的剖面进行了量测,所量测的剖面虽然只是整个斜坡的一部分,与经验数据相比,仍表现出高陡的特征,而且很多边坡在既高且陡的形态下仍能保持稳定。本文以极限平衡理论为基础,采用多种方法对这类边坡的稳定性进行计算分析,求出边坡的安全系数。考虑各种地震烈度下边坡的稳定性,得出这些边坡的安全系数与地震加速度具有严格的指数相关关系。 相似文献
4.
Holly L Ricks 《Tetrahedron letters》2004,45(16):3229-3232
An N,N′-diphenyl urea was designed as a model system for aggregation phenomenon in poly(phenyleneethynylenes) (PPEs). The unmethylated N,N′-diphenyl urea adopts an open, unfolded conformation in which the two diphenyl acetylene fluorophores are far enough away, mimicking the unaggregated state. Dimethylation forces the aromatic surfaces together into π-π contact, mimicking the aggregated state of PPEs. Analogous to bulk PPEs, this model system shows dramatic differences in quantum yield between the folded and unfolded states, with the unfolded urea having greater than 400-fold higher fluorescence quantum yield than its folded equivalent. 相似文献
5.
Uranium and uranium dioxide carbonyl cations produced by laser vaporization are studied with mass-selected ion infrared spectroscopy in the C-O stretching region. Dissociation patterns, spectra, and quantum chemical calculations establish that the fully coordinated ions are U(CO)(8)(+) and UO(2)(CO)(5)(+), with D(4d) square antiprism and D(5h) pentagonal bipyramid structures. Back-bonding in U(CO)(8)(+) causes a red-shifted CO stretch, but back-donation is inefficient for UO(2)(CO)(5)(+), producing a blue-shifted CO stretch characteristic of nonclassical carbonyls. 相似文献
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The infrared photodissociation spectra (IRPD) in the 700 to 4000 cm(-1) region are reported for H+ (CO2)n clusters (n = 1-4) and their complexes with argon. Weakly bound Ar atoms are attached to each complex upon cluster formation in a pulsed electric discharge/supersonic expansion cluster source. An expanded IRPD spectrum of the H+ (CO2)Ar complex, previously reported in the 2600-3000 cm(-1) range [Dopfer, O.; Olkhov, R.V.; Roth, D.; Maier, J.P. Chem. Phys. Lett. 1998, 296, 585-591] reveals new vibrational resonances. For n = 2 to 4, the vibrational resonances involving the motion of the proton are observed in the 750 to 1500 cm(-1) region of the spectrum, and by comparison to the predictions of theory, the structure of the small clusters are revealed. The monomer species has a nonlinear structure, with the proton binding to the lone pair of an oxygen. In the dimer, this nonlinear configuration is preserved, with the two CO2 units in a trans configuration about the central proton. Upon formation of the trimer, the core CO2 dimer ion undergoes a rearrangement, producing a structure with near C2v symmetry, which is preserved upon successive CO2 solvation. While the higher frequency asymmetric CO2 stretch vibrations are unaffected by the presence of the weakly attached Ar atom, the dynamics of the shared proton motions are substantially altered, largely due to the reduction in symmetry of each complex. For n = 2 to 4, the perturbation due to Ar leads to blue shifts of proton stretching vibrations that involve motion of the proton mostly parallel to the O-H+-O axis of the core ion. Moreover, proton stretching motions perpendicular to this axis exhibit smaller shifts, largely to the red. Ab initio (MP2) calculations of the structures, complexation energies, and harmonic vibrational frequencies are also presented, which support the assignments of the experimental spectra. 相似文献
8.
Of the three closo-carborane isomers (C2B10H12), closo-1,2-carborane has been used most widely in the synthesis of carboranyl amines. However, closo-1,2-carboranes are prone to deboronation to nido-7,8-carborane under various conditions including attack by basic amino groups. In order to overcome this problem, closo-1,7-carboranyl ethyl-, propyl-, and butylamine were synthesized, which should be more stable towards basic deboronation than their closo-1,2-carboranyl counterparts. These closo-1,7-carboranyl amines (5, 18 and 19) were synthesized using two different methods, both starting from the corresponding closo-1,7-carboranyl alkyl iodides (3, 14 and 15). One of the carboranyl alkyl amine (5) was conjugated with folic acid to form a closo-1,7-carborane-folic acid bioconjugate (20). 相似文献
9.
Miranda and Persson classified all extremal rational elliptic surfaces in characteristic zero. We show that each surface in Miranda and Persson's classification has an integral model with good reduction everywhere (except for those of type X 11(j), which is an exceptional case), and that every extremal rational elliptic surface over an algebraically closed field of characteristic p > 0 can be obtained by reducing one of these integral models mod p. 相似文献
10.
John F. LeBlanc Annette Ricks Leitze Charles E. Emenaker 《School science and mathematics》1995,95(4):175-177
Many elementary school teachers face severe time constraints working individually with students who need extra help or attention in mathematics. Sometimes, children who need this attention do not receive it. At the same time, critics of teacher education programs contend that preservice teachers do not receive enough hands-on experience teaching children. The Mathematics Tutorial Program is one attempt to address both of these issues. In this program, elementary grade children are identified by their classroom teachers as needing extra help in mathematics. They are paired with preservice elementary school teachers. Each preservice teacher tutors one or more elementary children for two 30-minute sessions each week for 6 to 24 weeks. They use manipulatives and a hands-on approach. The tutors reported professional gains from their contacts with classroom teachers, mathematics educators, and elementary children. Classroom teachers involved with the program commented on the children's improved selfesteem and confidence in mathematics. The children eagerly looked forward to the time with their tutors. 相似文献