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991.
聚偏氟乙烯全反式分子链振动模式的研究   总被引:2,自引:0,他引:2  
利用ab initio分子轨道计算,对β相聚偏氟乙烯(PVDF)的全反式分子链进行了结构优化,计算值和实验值基本符合,且发现C-C-C键角有两种不同的值,112.8°和113.3°.对该分子的频率进行了计算,得到了红外强度谱.在400~4 000 cm-1范围内,对30 μm厚的聚偏氟乙烯取向膜和取向极化膜进行了红外光谱的测量,红外吸收光谱和红外强度谱基本一致.把所有振动模式分成六个系列:系列Ⅰ(544~415 cm-1),系列Ⅱ(913~792 cm-1),系列Ⅲ(1 353~998 cm-1),系列Ⅳ(1 458~1 361 cm-1),系列Ⅴ和系列Ⅵ.其中只有系列Ⅲ能改变分子的电偶极矩,该系列振动模式和β相的PVDF的自发极化有着密切的关系.  相似文献   
992.
Preparation, Crystal Structures, Vibrational Spectra, and Normal Coordinate Analysis of trans-(PNP)[TcCl4(Py)2] and trans-(PNP)[TcBr4(Py)2] By reaction of (PNP)2[TcX6] with pyridine in the presence of [BH4]? (PNP)[TcX4(Py)2], X = Cl, Br, are formed. X-ray structure determinations on single crystals of these isotypic TcIII complexes (monoclinic, space group P21/n, Z = 2, for X = Cl: a = 13.676(4), b = 9.102(3), c = 17.144(2) Å, β = 91.159(1)°; for X = Br: a = 13.972(2), b = 9.146(3), c = 17.285(4) Å, β = 90.789(2)°) result in the averaged bond distances Tc? Cl: 2.386, Tc? Br: 2.519, Tc? N: 2.132(3) (X = Cl) and 2.143(4) Å (X = Br). The two pyridine rings are coplanar and vertical to the X? Tc? X-axes, forming angles of 42.28° (X = Cl) and 43.11° (X = Br). Using the molecular parameters of the X-ray structure determination and assuming D2h point symmetry, the IR and Raman spectra are assigned by normal coordinate analysis based on a modified valence force field. Good agreement between observed and calculated frequencies is obtained with the valence force constants fd(TcCl) = 1.45, fd(TcBr) = 1.035, fd(TcN) = 1.37 (X = Cl) and 1.45 mdyn/ Å (X = Br), respectively.  相似文献   
993.
The infrared spectrum of sulfamoil chloride in the liquid phase was reinvestigated; the infrared and Raman spectra of the solid phase have also been obtained. A complete assignment of the observed bands is proposed. A subsequent normal coordinate analysis was performed. The experimental data are compared to results of ab initio and DFT (density functional theory) calculations. According to the experimental and theoretical results the main conformer of ClSO2NH2 possesses an anti conformation (Cs symmetry, S---Cl single bond in anti position with respect to the nitrogen lone pair).  相似文献   
994.
The scaling factors for the vibrational frequencies and zero-point vibrational energies evaluated at various combinations of recently developed exchange-correlation functionals and various basis sets are reported. The exchange-correlation functionals considered are B972, B98, HCTH, OLYP, O3LYP, G96LYP, PBE0 and VSXC functionals; the basis sets employed are 3-21G, 6-31G*, 6-31G**, 6-31+G, 6-311G*, 6-311G**, 6-311G(df,p), 6-311+G(df,p), cc-pVDZ and aug-cc-pVDZ. The experimental harmonic frequencies of 122 small molecules and the zero-point vibrational energies of 39 small molecules are used to determine the scaling factors through the least-square fitting procedure. It was found that the scaling factors do not depend significantly on the basis sets considered. The vibrational frequency scaling factors evaluated by using the B98 and PBE0 functionals are recommended on the basis of smallest root mean square error. The zero-point vibrational energy scaling factors evaluated from the B972 functional with Pople's double-zeta basis set and the HCTH functional with Pople's triple-zeta basis set are recommended on the basis of smallest root mean square error.  相似文献   
995.
Rubidium dihydrogentricyanomelaminate semihydrate Rb[H2C6N9] · 1/2 H2O was obtained as colorless rod‐like single crystals from a solution of Rb3[C6N9] · H2O and 0.1 M HCl after water evaporation at room temperature. According to the X‐ray single‐crystal structure determination (Rb[H2C6N9] · 1/2 H2O: C2/c (no. 15), a = 2007.4(3) pm, b = 512.2(1) pm, c = 2168.0(4) pm, β = 111.66(2)°, Z = 8, R1 = 0.059, 2391 independent reflections, 159 parameters) Rb+ and cyclic planar [H2C6N9] ions as well as hydrate water molecules occur in the crystal. Rb[H2C6N9] · 1/2 H2O was investigated by FTIR and Raman spectroscopy, TG measurements and temperature‐dependent X‐ray powder diffraction. According to the thermoanalytic investigations, dehydration of Rb[H2C6N9] · 1/2 H2O starts above 60 °C and is finished below 250 °C.  相似文献   
996.
The third Li+ translational mode of lattice vibration of lithium hydrogen oxalate monohydrate has been assigned to the band at about 383/360 cm–1 taking the characteristic6Li/7Li isotope band shifts into consideration.
Über die Zuordnung einer der drei translatorischen Li+-Moden in Lithiumhydrogenoxalat-Monohydrat (Kurze Mitteilung)
Zusammenfassung Es wurden die IR-Spektren der Li- und H-isotopen Lithiumhydrogenoxalat-Monohydrate bei 100 K und 300 K gemessen. Einer der drei translatorischen Moden wird einer Bande zugeordnet, die bei Berücksichtigung der6Li/7Li Isotopenverschiebung bei 383/360 cm–1 auftritt.
  相似文献   
997.
Selenites of ethylene diamine, propylene diamine and butylene diamine were prepared by crystallization from aqueous solution. The crystal structure was solved for all the substances. Ethylene diammonium(2+) selenite crystallizes in the orthorhombic space group P21212, a=11.3710(2) Å, b=11.4390(5) Å, c= 4.6290(4) Å, V= 602.11(6) Å3, Z=4, R=0.0341 for 5729 observed reflections. 1,3-Propylene diammonium(2+) selenite dihydrate crystallizes in the monoclinic space group C2/c, a=16.241(14) Å, b=6.673(5) Å, c=17.731(14) Å, β=110.88(2)°, V=1795(3) Å3, Z=8, R=0.0271 for 12,233 observed reflections. 1,4-Butylene diammonium(2+) selenite dihydrate crystallizes in the monoclinic space group P21/c, a=6.686(5) Å, b=16.597(14) Å, c=9.282(8) Å, β=96.653(14)°, V=1023.2(14) Å3, Z=4, R=0.0465 for 2918 observed reflections. The FTIR an FT Raman spectra of all the compounds were recorded and interpreted. The thermoanalytical properties were studied by the TG, DTG, and DTA methods in the 293–633 K temperature range. DSC measurements were carried out in the range from 98 K to the temperature of decomposition of the compounds. No thermal effect indicating a phase transition was observed in this temperature region.  相似文献   
998.
Summary. The cohesion potential energy of the crystal of one enantiomer of ethyl 3-cyano-3-(3,4-dimethyloxyphenyl)-2,2,4-trimethylpentanoate, −47.7 ± 0.1 kJ mol−1 (0–90°C), was found out from the heat of sublimation (123.2 ± 5.1 kJ mol−1, 78.6°C) and the kinetic energies for the gas phase and the crystal. It was found that the entropy function of Debye’s theory of solids mathematically agreed with the vibrational entropy of the gas (variationally obtained), allowing to disclose the vibrational energy using the Debye energy function (E vib 835.0 kJ mol−1 (78.6°C), E 0 included). E kin for the crystal (771.1 kJ mol−1 (78.6°C)) was obtained by Debye’s theory with the experimental heat capacity. The cohesion energy represented a moderate part of the sublimation energy. The cohesion energy of the racemic crystal, −44.2 kJ mol−1, was obtained by the heat of formation of the crystal in the solid state (3.0 kJ mol−1, 83.3°C) and E kin for the crystal (by Debye’s theory). The decrease in cohesion on formation of the crystal accounted for the energy of formation. The change in potential energy on liquefaction of the racemate from the gas state was disclosed obtaining added-up E vib + rot for the liquid in the way as to E vib for the gas, the Debye entropy function being increasedly suited for the liquid (E vib + rot 763.4 kJ mol−1 (115.4°C)). Positive ΔE pot, 13.0 kJ mol−1, arised from the increase in electronic energy (Δ l νmean − 154.3 cm−1, by the dielectric nature of the liquid), added to the cohesion energy.  相似文献   
999.
Preparation, Crystal Structures, Vibrational Spectra, and Normal Coordinate Analysis of four Linkage Isomeric Trichlorotrirhodanoosmates(IV) By treatment of fac-[OsCl3I3]2? with (SCN)2 in dichloromethane the linkage isomers fac-[OsCl3(NCS)3]2? ( 1 ), mer-[OsCl3(NCS)2c(SCN)]2? ( 2 ), mer-[OsCl3(NCS)(SCN)2t]2? ( 3 ), and mer-[OsCl3(NCS)(SCN)2c]2? ( 4 ) are formed which have been separated by ion exchange chromatography on diethylaminoethyl cellulose. X-Ray structure determinations have been performed on single crystals of fac-(Ph4As)2[OsCl3(NCS)3] (triclinic, space group P1 , a = 12.142(5), b = 13.233(5), c = 19.300(5) Å, α = 98.642(5)º, β = 100.509(5)º, γ = 112.514(5)º, Z = 2), mer-(Ph4As)2[OsCl3(NCS)2c (SCN)] · acetone (triclinic, space group P1 , a = 11.707(5), b = 13.238(5), c = 19.048(5) Å, α = 75.960(5)º, β = 88.981(5)º, γ = 69.999(5)º, Z = 2), mer-(Ph4As)2[OsCl3(NCS)(SCN)2 t] (triclinic, space group P1, a = 10.6861(12), b = 11.6587(5), c = 12.5232(5) Å, α = 112.069(8)º, β = 95.052(8)º, γ = 92.559(7)º, Z = 1) and mer-(Ph4As)2[OsCl3(NCS)(SCN)2 c] · 2acetone (triclinic, space group P1 , a = 11.444(5), b = 14.661(5), c = 15.830(5) Å, α = 75.790(5)º, β = 80.273(5)º, γ = 75.205(5)º, Z = 2). The complex anions are completely ordered. The via N or S coordinated thiocyanate groups are located nearly direct above one of the cis-positioned Cl ligands with Os? N? C angles of 169.1º, 171.5º, 175.7º ( 1 ), 175.6º, 178.6º ( 2 ), 172º ( 3 ), and 173.1º ( 4 ) and Os? S? C angles of 106.2º ( 2 ), 106.1º, 106.6º ( 3 ), 105.1º, and 108.2º ( 4 ). Using the molecular parameters of the X-Ray determinations the low temperature (10 K) IR and Raman spectra of the (n-Bu4N) salts of all four linkage isomers have been assigned by normal coordinate analyses based on a modified valence force field. The valence force constants are fd(OsN) = 1.71 ( 1 ), 1.46 and 1.62 ( 2 ), 1.69 ( 3 ), and 1.61 ( 4 ), fd(OsS) = 1.27 ( 2 ), 1.36 ( 3 ), 1.32, and 1.49 mdyn/Å ( 4 ). Taking into account increments of the trans influence a good agreement between observed and calculated frequencies is achieved.  相似文献   
1000.
The binary germanides M12Ge17 and M4Ge9 (M ? Na, K, Rb, Cs) and the stannides M12Sn17 and M4Sn9 (M ? K, Rb, Cs) were identified by a combination of direct synthesis, thermogravimetric analysis, vibrational spectroscopy, X-ray powder data and single crystal structure analysis. The M12E17 phases contain the cluster anions [E9]4? and [E4]4? in the ratio 1:2, forming a hierarchical structure with the cluster anions at the atomic positions of the hexagonal Laves phase MgZn2. Like the M4E4 phases, the M4Ge9 compounds are hierarchical derivatives of the cubic Cr3Si structure but with [Ge9]4? anions. The thermogravimetric analyses give strong evidence for the existence of at least one more phase with [E9]4? and [E4]4? clusters and of the clathrate phases M6E136 in addition to the well-known M8E442 chlathrates.  相似文献   
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