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The energy of a disubstituted molecule has often been approximated by simple electrostatic formulas that represent the substituents as poles or dipoles. Herein, we test this approach on a new model system that is more direct and more efficient than testing on acid-base properties. The energies of 27 1,4-derivatives of bicyclo[2.2.2]octane were calculated within the framework of the density functional theory at the B3LYP/6-311+G(d,p) level; interaction of the two substituents was evaluated in terms of isodesmic homodesmotic reactions. This interaction energy, checked previously on some experimental gas-phase acidities, was considered to be accurate and served as reference to test the electrostatic approximation. This approximation works well in the qualitative sense as far as the sign and the order of magnitude are concerned: beginning with the strongest interaction between two poles, a weaker interaction between pole and dipole, and the weakest between two dipoles. However, all the electrostatic calculations yield energies that are too small, particularly for weak interaction, and this fundamental defect is not remedied by some possible improvements. In particular, variation of the effective permittivity would require a physically impossible value less than unity. The explanation must lie in a more complex distribution of electron density than anticipated in the electrostatic model. It also follows that possible conclusions about the transmission of substituent effects "through space" have little validity. 相似文献
44.
T. Al Adlouni F. Meyer C. Meyer A. Fayt 《International Journal of Infrared and Millimeter Waves》1986,7(3):405-419
The perpendicularv
8 band lying in the 1000–1100 cm–1 region has been studied from infrared and laser Stark, spectra. We were interested in the part of spectrum corresponding to the spectral range of the 9 m CO2 laser lines. Assignments of rovibrational lines with J'<40 and K'<6 have been made. About 100 Stark resonances have been assigned to 12 rovibrational transitions. Effective molecular constants and dipole moment have been determined with high accuracy. A list of close resonances with CO2 laser lines is given and may be used for optical pumping experiments. 相似文献
45.
Stefka Taneva Mira Busheva 《Journal of photochemistry and photobiology. B, Biology》1991,10(4):315-327
Electric light scattering and microelectrophoresis were applied to investigate the electric moments (permanent dipole moment and electric polarizability and electrophoretic mobility of envelope-free chloroplasts and photosystem II (PS II particles. The effect of the removal of the extrinsic polypeptides (18, 24 and 33 kDa) on the electric moments was also studied. A significant difference was observed between the orientation behaviour of chloroplasts and PS II preparations. The data indicate that the permanent and induced dipole moments contribute to the orientation of the PS II particles, whereas chloroplasts possess induced dipole moment only.
NaCl and Tris treatments of PS II preparations influence both the transverse permanent dipole moment and the electric polarizability of PS II particles. The increase in the electrophoretic mobility of PS II particles on removal of the extrinsic proteins corresponds to an increase in the electric polarizability value, demonstrating its interfacial nature. 相似文献
46.
A. N. Ageev A. A. Aratskova L. D. Belyakova T. N. Gvozdovich A. V. Kiselev Ya. I. Yashin J. Kàlal F. Švec 《Chromatographia》1983,17(10):545-548
Summary The retention of benzene derivatives with nonpolar and polar substituents on a porous methacrylate copolymer containing epoxy groups using both nonpolar and polar eluents was investigated. When n-hexane is used as the eluent, the retention of n-alkylbenzenes and polymethylbenzenes is weaker than that of benzene. In the case of benzene derivatives containing polar functional groups their capacity ratios (k) on this porous polymer increases approximately linearly with the increase of the adsorbate molecules dipole moment. The retention characteristics of the methacrylate copolymer were compared with that of a styrene-divinylbenzene copolymer and silica gels with a hydroxylated surface and with a surface modified by chemically bonded alkylsilyl groups. 相似文献
47.
The mean-square molecular dipole moments 〈μ2〉 of carbazole, N-ethylcarbazole and of the sequence of poly(epoxypropylcarbazole) (PEPCa) oligomers of various molecular weights have been evaluated in solutions of these organic compounds in dioxan. For PEPCa the values of 〈μ2〉 have also been determined in the solid state. On the basis of the experimental results and of molecular mechanics calculations it has been shown that the orientation of the lateral group of PEPCa favors noninteracting racemic dyads. The temperature-dependence of the effective dipole moment of solid PEPCa follows the Onsager theory above 295 K. 相似文献
48.
Wiosetek-Reske AM Wysocki S Bak GW 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,62(4-5):1172-1178
The absorption and fluorescence spectra of N-nonyl acridine orange are determined at room temperature (298 K) in cyclohexane, benzene, carbon tetrachloride, chloroform, chlorobenzene and dichloromethane. The ground state of dipole moment was obtained by impedance measurements using Guggenheim-Debeye's method. The experimental excited state dipole moment of N-nonyl acridine orange was determined using Bakhshiev's and Kawski-Chamma-Viallet's formulae and solvent polarity parameter proposed by Reichardt. These experimental results were completed with theoretical results using quantum chemical methods. The experimental (muexp=10.76 D) and theoretical (mucal=9.9 D) dipole moments in the ground and excited state (muexp*=14.56 D) were compared. 相似文献
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The intergrowth of 1,10-decanedicarboxylic acid and urea give infinite hydrogen-bonded chains of the guest included in the hexagonal urea host. A deuterium high-resolution solid-state NMR study of the selectively deuterated intergrowth compound 1,10-decanedicarboxylic acid/hydrogenated urea at variable temperature in the range 90 < or = T < or = 300 K was performed on a single crystal. The analysis of the second moment as a function of temperature is shown to be compatible with the known phase transition occurring near T(c) = 203 K. Moreover, the spectra indicate that the orientational disorder is strong, and is compared to an axial uniform disorder. For this purpose, the general equation for the second moment of a system with uniform two-dimensional axial orientational disorder is given, and a method to take into account the non-uniform excitation of the pulse sequence is proposed. 相似文献