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11.
12.
Bingxin LiuYoshio Tatamitani Jun ShimadaTeruhiko Ogata 《Journal of Molecular Spectroscopy》2002,211(1):99-106
The microwave spectrum of the 35Cl and 37Cl isotopic species of 1-chloro-1,1,2-trifluoroethane (HCFC-133b) has been investigated in the frequency region 10 to 50 GHz using a Stark modulation microwave spectrometer. A pulsed jet Fourier transform microwave spectrometer was also used for the measurement of hyperfine splittings. A least-squares analysis of the observed b-type Q- and R-branch transition frequencies gave rotational and centrifugal distortion constants and components of the chlorine nuclear quadrupole coupling constant tensors in the principal axes system as follows: A=4625.161 (3) MHz, B=2004.127 (2) MHz, C=1875.813 (2) MHz, ΔJ=0.144 (9) kHz, ΔJK=1.0748 (8) kHz, ΔK=1.57 (1) kHz, δJ=0.01376 (4) kHz, δK=−0.146 (4) kHz, χaa=−57.958 (10) MHz, χbb=21.231 (11) MHz, and χcc=36.727 (11) MHz for 35ClCF2CH2F species, and A=4607.684 (6) MHz, B=1960.565 (2) MHz, C=1834.823 (2) MHz, ΔJ=0.106 (7) kHz, ΔJK=1.022 (3) kHz, ΔK=1.48 (1) kHz, δJ=0.0142 (2) kHz, δK=−0.18 (2) kHz, χaa=−46.268 (11) MHz, χbb=17.319 (13) MHz, and χcc=28.950 (13) MHz for 37ClCF2CH2F species. The structural parameters are calculated from the observed six rotational constants by assuming the partial structure of ab initio calculation. The electronic properties of the C-Cl bond are evaluated from the observed nuclear quadrupole constants of chlorine. These molecular properties are compared with those of other related molecules. 相似文献
13.
We obtain expressions for the energy spectrum widths of Rayleigh waves corresponding to their deformational coupling to Fermi and Boltzmann electrons in a two-dimensional layer near the surface of a semibounded solid. We evaluate the nonequilibrium energy of Rayleigh waves that depends on these widths and is caused by the same coupling to the corresponding hot electrons. We show that this energy is independent of the degeneracy degree of the electrons and is given by the mean energy of free Rayleigh waves heated up to temperature of the electrons. We find conditions under which the thermodynamics is determined by this nonequilibrium energy of Rayleigh waves in films of a certain thickness with Fermi electrons near the surface and by the equilibrium energy of bulk phonons in thicker samples. All the results are obtained using the Keldysh diagram technique applied to the case of semibounded media. 相似文献
14.
双氯芬酸钠与牛血清白蛋白结合反应的特征 总被引:2,自引:0,他引:2
在模拟人体生理条件下,采用荧光光谱和紫外 可见吸收光谱法研究了双氯芬酸钠与牛血清白蛋白的结合反应.实验结果显示,双氯芬酸钠对牛血清白蛋白有较强的荧光猝灭作用,该猝灭过程主要为静态荧光猝灭过程;二者结合常数KLB=2.167×105mol·L-1;二者的结合位置距212位色氨酸2.13nm;同时,由结合反应的热力学参数得出二者作用力主要是氢键或VanderWall's力. 相似文献
15.
富勒烯 (C60 /C70 )与N ,N ,N′ ,N′ 四 (对甲苯基 ) 4,4′ 二胺 1,1′ 二苯硒醚 (TPDASe)间在激光光诱导条件下 ,发生了分子间的电子转移过程 .在可见 -近红外区 ( 60 0~ 12 0 0nm) ,观测到了TPDASe阳离子自由基、富勒烯 (C60 /C70 )激发三线态和阴离子自由基 ,在苯腈溶液中 ,观测瞬态谱测定了电子从TPDASe转移到富勒烯 (C60 /C70 )激发三线态的量子转化产率(ΦTet)和电子转移常数 (Ket) . 相似文献
16.
17.
A. A. Zazhogin A. P. Zazhogin A. I. Komyak A. I. Serafimovich 《Journal of Applied Spectroscopy》2003,70(6):827-831
Based on the analysis of electronic absorption and luminescence spectra, the processes of complexing in an aqueous solution of uranyl nitrate hexahydrate (UO2(NO3)2·6H2O) on gradual addition of small amounts of acetone have been investigated. In a pure aqueous solution, uranyl exists as the UO2·5H2O complex. It is shown that addition of acetone to the solution leads to displacement of some water molecules from the first coordination sphere of uranyl and formation of uranyl nitrate dihydrate complexes, UO2(NO3)2·2H2O. It has been established that the stability of these complexes is determined by the decrease in both the water activity and the degree of hydration of uranyl and nitrate. This is the result of the local increase in the concentration of the molecules of acetone (due to its hydrophobicity) in those regions of the solution in which there are uranyl and nitrate ions. The experimental facts supporting the proposed mechanism are given. 相似文献
18.
M. Faucher D. Garcia E. Antic-Fidancev M. Lemaitre-Blaise 《Journal of Physics and Chemistry of Solids》1989,50(12)
Some structural and spectroscopic features of rare earth orthoaluminates are examined.The trigonal→ orthorhombic transition is studied in a series of NdxSm1−xAlO3 compounds. The evolution of the crystal structure is followed by X-ray analysis and optical absorption. The free ion and crystal field parameters of Nd3+ (4f3 configuration) are determined in LuAlO3:Nd3+.The anomaly of the calculated splitting of the
levels is slight, but well characterized in NdAlO3. The spin correlated crystal field and orbitally correlated crystal field models are tested as well as an empirical correction which was proposed earlier. 相似文献
19.
Using the DFT/B3LYP method with a 6-31G(d) basis set, the structure, normal vibration frequencies, and the absolute band intensities in the IR spectra of the chlorin molecule and its four symmetric isotopomers have been calculated. Scaling of the force field by the Pulay method in independent and natural coordinates has been carried out. A method for obtaining effective force fields without using experimental data on the fundamental vibration frequencies is proposed. By comparing the vibration modes and constructing special matrices, complete assignment of the fundamental frequencies of porphin and chlorin has been carried out. It has been shown that the majority of porphin macroring vibrations upon pyrrolenine ring hydrogenation are frequency-characteristic and only 12 vibrations change considerably. A frequency correlation with regard for the mode transition between chlorin and all its isotopomers under consideration has been established. Comparative analysis of the force fields of porphin and chlorin in dependent natural coordinates has revealed the unique nonlocal character of the change in force constants of the macroring upon hydrogenation of one pyrrolenine ring. Modeling of the IR spectra of chlorin and its isotopomers has been performed. Assignment and interpretation of the normal vibrations of the molecules under consideration have been carried out. 相似文献
20.
The structure, harmonic frequencies, and nonresonance Raman intensities for porphin, tetraazaporphin (TAP), and three of its isotopomers are calculated by the density-functional theory of B3LYP/6-31G(d). Scaling of force constants for porphin in nonredundant natural coordinates is performed. The scaling factors obtained were used to predict the force field and normal modes of TAP and three of its isotopomers. Two alternative methods are used to carry out reliable assignment of the TAP frequencies: wavenumber-linear scaling method and frequency-shift method. There is good agreement between the frequencies predicted within the framework of the three methods used. The conservativeness of the out-of-plane B
2g
- and B
3g
-modes for porphin and TAP is examined. The Raman spectrum for TAP is simulated. A refinement of the assignment of the experimental frequencies for TAP of even symmetry types on the basis of the calculations performed is made. 相似文献