C6H6可见光与红外跃迁强度的代数方法计算

Based on the wavefunctions obtained in the calculation of C-H stretching overtones of C6H6 and C6D6 molecules,the visible and infrared transition intensities of the molecules for C-H stretching overtones up to as high as v=0 are described by the Iachello-Oss algebraic model on the symmetric bases. The formula for Raman transition is also given. The operators for the transition are constructed according to the symmetry of the molecule. The construction of the symmetric bases is greatly simplified by using the symmetrized boson representation technique. Combining with the overtones calculation,the present work shows the vibration mode of C-H stretching is the local mode,which is consistent with other works. The agreement between the calculated results and observations is very good. The agreement indicates that the coupling between C-H stretching mode and other modes is weak or the coupling effects can be absorbed in the adjustment of parameters. The high precision calculation of the properties of molecules can be achieved by the algebraic model with fewer parameters compared with the traditional method. It also indicates that the combination of algebraic model and the symmetrized boson representation technique is a very powerful tool for describing the vibration of molecules.     

Mass spectrometric studies of structural isomers—II: Mono-and bicyclic C6H10 molecules

The electron-impact-induced ionization and fragmentation of six C₆H₁₀ structural isomers have been studied in order to determine the effect of isomerism upon their mass spectrometric behavior. The 70 eV mass spectra, metastable transitions and appearance potentials of the principal ions are reported. Significant differences between the mass spectra of the six isomers were observed; however, metastable transition and appearance potential data indicate that the fragmentation path-ways are the same for all the C₆H₁₀ molecules. Experimentally determined ionization potentials for the structural isomers are presented and compared to ionization potentials calculated by the bond orbital method. Utilizing fragmentation pathways deduced from general features in the mass spectra and from observed metastable transitions, we calculated heats of formation (ΔH_f) for the observed principal ions and compared these values to ΔH_f values for isomeric ions from other molecules.     

Schwingungs-Resonanz-Raman-Spektren von [n-(C4H9)4N]2[OsBr6] bei 77 K

Vibrational Resonance Raman Spectra of [n-(C₄H₉)₄N]₂[OsBr₆] at 77 K A rotating Raman cell in the 180° scattering geometry is described. It permits the measurement of Raman spectra of deeply coloured solids and liquids at the temperature of liquid nitrogen. Meaningful polarization measurements on solid samples are obtained by the use of optically isotropic pellets of tetraalkylammonium complex salts. In the solid state [n-(C₄H₉)₄N]₂[OsBr₆] displays a rigorous resonance Raman effect. Especially the excitation at 454.4 and 457.9 nm coincides with an intense electric dipole allowed charge-transfer transition of the anion, so that as far as nine overtones of the totally symmetric stretching vibration A_1g and many combination tones of this vibration with the other ra-active fundamentals are to be observed. The determination of the spectroscopic constants ω₁ and x₁₁ demonstrates, that the deviations from the harmonic oscillator are within the limit of error.     

Algebraic expressions of irreducible bases for molecules C20H20, C80, and C240

Using the symmetrized boson representation technique, concise algebraic expressions of the irreducible bases symmetry adapted to the group chain I_h⊃C₅ for the fullerene molecules C₂₀H₂₀, C₈₀, and C₂₄₀ are derived for the most general cases and those for any specific case can be derived from them easily without a projection procedure. ©1999 John Wiley & Sons, Inc. Int J Quant Chem 73: 283–297, 1999     

Pr6C2‐Doppeltetraeder in Pr6C2Cl10 und Pr6C2Cl5Br5

Pr₆C₂‐Bitetrahedra in Pr₆C₂Cl₁₀ and Pr₆C₂Cl₅Br₅ The compounds Pr₆C₂Cl₁₀ and Pr₆C₂Cl₅Br₅ are prepared by heating stoichiometric mixtures of Pr, PrCl₃, PrBr₃ and C in sealed Ta capsules at 810 ? 820 °C. They form bulky transparent yellow to green and moisture sensitive crystals which have different structures: space groups C2/c, (a = 13.687(3) Å, b = 8.638(2) Å, c = 15.690(3) Å, β = 97.67(3)° for Pr₆C₂Cl₁₀ and a = 13.689(1) Å, b = 10.383(1) Å, c = 14.089(1) Å, β = 106.49(1)° for Pr₆C₂Cl₅Br₅). Both crystal structures contain C‐centered Pr₆C₂ bitetrahedra, linked via halogen atoms above edges and corners in different ways. The site selective occupation of the halogen positions in Pr₆C₂Cl₅Br₅ is refined in a split model and analysed with the bond length‐bond strength formalism. The compound is further characterized via TEM investigations and magnetic measurements (μ_eff = 3.66 μ_B).     

[C6H6, C3H7 +]and [C6H7 +, C3H6] ion-neutral complexes intermediate in the reactions of protonated propylbenzenes

From the mass-analysed ion kinetic energy spectra of labelled ions, kinetic energy releases and thermodynamic data, it is proved that protonated n-propylbenzene (1) isomerizes into protonated isopropyl benzene (2). It is also shown that the dissociation of the less energetic metastable ions of (2), leading to [iso-C₃H₇]⁺ and [C₆H₇]⁺ product ions, is preceded by H exchange. This H exchange involves two interconverting ion-neutral complexes [C₆H₆, iso-C₃H₇⁺] (2π) and [C₆H₇⁺, C₃H₆] (2α).     

Hydrogen migrations in mass spectrometry. IV—formation of [C6H7]+ in the chemical ionization mass spectra of alkylbenzenes

Using specific deuterium labelling the mechanisms of the olefin elimination reactions leading to formation of [C₆H₇]+ in the H₂ and CH₄ chemical ionizatin mass spectra of ethylbenzene and n-propylbenzene (and to [C₂H₅C₆H₆]+ in the CH₄ chemical ionization mass spectra) have been investigated. The results show that the reaction does not occur by specific migration of H from the β position of the alkyl group to the benzene ring. For ethylbenzene 23–29% of the migrating H originates from the α-position, while for n-propylbenzene H migration from all propyl positions is observed in the approximate ratio, position 1:position 2:position 3=0.30:0.22:0.48. It is proposed that the results can be explained on the basis of competing H migration from each alkyl position involving cyclic transition states of different ring sizes, rather than by H randomization within the alkyl chain.     

ESR studies on the structure of C6F−6 anions

Rigid solution spectra for C₆F^?₆ and C₄F^?₈ are compared, and it is concluded that C₆F^]t-₆ cannot have the planar, σ^* structure previously postulated. Instead, a puckered-ring structure with σ and pseudo π delocalisation is postulated.     

Charge inversion as a structural probe for C6H 5 + and C6H 6 +· cations

Charge reversal (⁺CR⁻) of cations to anions can be used to structurally differentiate isomeric C₆H₅⁺ and C₆H₆^+· hydrocarbon ions by means of tandem mass spectrometry. In view of the manifold of possible isomers, only a few prototype precursors are examined. Thus, charge inversion demonstrates that electron ionization of 2,4-hexadiyne yields an intact molecular ion, whereas the charge inversion spectra of C₆H₆^+· obtained from benzene, 1,5-hexadiyne, and fulvene are identical within experimental error. Similarly, the ⁺CR⁻ spectrum of the C₆H₅⁺ cation generated by dissociative ionization of 2,4-hexadiyne is significantly different from the ⁺CR⁻ spectrum of C₆H₅⁺ obtained from iodobenzene, suggesting the formation of a 2,4-hexadiynyl cation from the former precursor. Although charge inversion of cations to anions has a low efficiency and requires large precursor ion fluxes, the particular value of this method is that the spectra may not just differ in fragment ion intensities, but these differences can directly be related to the underlying ion structures.     

Preparation of spiro-cyclic organic polysulfanes of type C6H10Sn and x-ray structural analysis of C6H10S11, a derivative of cyclo-dodecasulfur

By reaction of (C₅H₅)₂Ti(μ-S₂)₂C₆H₁₀ 3 with S₂Cl₂ 7,8,9,10,11,12-hexathiaspiro-[5.6]dodecane 4 is prepared (yield 51%) and characterized by UV, IR, Raman, mass, and NMR spectra (¹H, ¹³C). The seven-membered CS₆ ring undergoes pseudorotation in solution. With S₇Cl₂ the complex 3 yields 7,8,9,10,11,12,13,14,15,16,17-undecathiaspiro[5.11]heptadecane 5 (yield 23%). The yellow, monoclinic crystals of 5 consist of spirocyclic C₆H₁₀S₁₁ molecules with the C₆ ring in a chair-conformation while the CS₁₁ ring is of the same conformation as cyclododecasulfur S₁₂. UV, IR, Raman, mass and NMR-spectra of 5 are reported. A mixture of dichlorosulfanes S_nCl₂ (n = 1 -8) reacts with 3 to give the homologous series C₆H₁₀S_m which was characterized by reversed-phase HPLC for m = 5 – 14.     

The isomerization mechanism of alkylamines: Structure of [C2H6N]+ and [C3H8N]+ fragment ions

The MIKE spectra of amines RCH₂NH₂ containing more than five carbon atoms exhibit m/z 44 and m/z 58 peaks. The structures of these [C₂H₆N]⁺ and [C₃H₈N]⁺ ions have been established by collisional activation spectra. The results are in agreement with the fragmentation mechanisms previously proposed.     

Absorption spectrum of Yb3+(4f13) IN[(C6H5)3PH]3 YbCl6

Optical absorption spectra taken at 300 and 77 K are reported for six-fold octahedrally coordinated Yb³⁺(4f¹³) in [(C₆H₅)₃PH]₃ YbCl₆. In addition to vibronic spectra we observe electronic transitions which suggest that inversion symmetry is lifted by a small distortion similar to that reported for the Nd³⁺(4f³) spectrum of the corresponding salt. The vibronic as well as the electronic transition have been analyzed on the basis of six-fold octahedral symmetry. The analysis appears reasonable and consistent in comparison with other rare-earth ions that have been studied in similar cubic and octahedral environments.     

Genesis of the phonon spectra of A2B4C 2 5 and A1B3C 2 6 crystals with a chalcopyrite lattice from the vibrational states of their sublattices

The phonon spectra of a series of A²B⁴C ₂ ⁵ and A¹B³C ₂ ⁶ crystals with the chalcopyrite structure are calculated in the Keating model in the basis set of polarization vectors of their sublattices. The dependences of frequency values and partial contributions of sublattices to the polarization vectors on the chemical composition are studied. The effect of the mass ratio and the strengths of covalent bonds between the compound components on the phonon spectrum formation is found.     

Photodissociation and structures of [C6H4]+ ˙ ions generated from cyanobenzene and other precursors

Previous work on the electron impact induced loss of hydrogen cyanide from the radical cations of cyanobenzene has revealed that ring opening is important in the formation of the corresponding [C₆H₄]^{+ ˙} ions. Photodissociation experiments now show that these [C₆H₄]^{+ ˙} ions and those generated from 2-ethynylpyridine, 1,3-hexadiyn-6-nitrile and 1,2-diiodobenzene all photodissociate in the visible region to [C₄H₂]^{+ ˙}. The corresponding photodissociation spectra are all the same and have a maximum at about 370 nm, in agreement with spectra of ions with three conjugated double or triple bonds. Owing to the high reactivity, the low photodissociation rate and, possibly, the internal energy of the ions, the photodissociation kinetics are too complicated to be solved. The experiments nevertheless show that at least a major fraction of the [C₆H₄]^{+ ˙} ions has a ring-opened structure. This conclusion is supported by MNDO calculations, which indicate that the heats of formation of the possible acyclic structures are about 150 kJ mol^?1 lower than those of the o-, m- and p-benzyne structures.     

New polymer-supported catalysts. (Polyvinylchloride-containing redox) catalyst cyclopentadienyl iron moiety: [η5C5H5Feη6C6(CH3)5CH2?]+

New polymer-supported catalysts that contain the redox cyclopentadienyl iron moiety [η⁵C₅H₅Feη⁶C₆(CH₃)₅CH₂? ]⁺ were prepared with polyvinylchloride (PVC) as support. The active center is attached as a pendant organometallic moiety in the side groups of the PVC chain. Metallocenic groups and the supported polymers with various Fe content were analyzed by spectroscopic techniques and by polarographic and cyclic voltammetry. The absorption spectra show a similar profile to that of the nonsupported cation, which indicates that the supported polymer contains side groups in the chain with metallocenic structures. The new polymer-supported catalysts were characterized by viscometric measurements and by differential calorimetry (DSC). A linear relationship between intrinsic viscosity/[η] and the Fe content was observed. The glass transition temperature (T_g) values are higher than those of PVC without modification.     

A structural investigation of [C6H6]2+ and [C6H6]+˙ ions involved in charge exchange reactions

Mass-analysed ion kinetic energy spectra for collisional activation (CA) of [C₆H₆]⁺˙ formed via electron capture by [C₆H₆]²⁺ ions in collision with neutral benzene molecules have been compared for the C₆H₆ isomers benzene, 1,5-hexadiyne and 2,4-hexadiyne. Comparisons of fragment abundance and total CA fragment yields were also made for [C₆H₆]⁺˙ ions generated by electron ionization (EI). CA conditions of ion velocity and collision gas pressure were identical in these comparisons. In general the fragment abundance patterns for the ions formed by charge exchange were very similar to those for singly charged benzene ions generated by EI. However, significant variations in CA fragment yield (the ratio of the total CA fragment ion abundance to the abundance of the incident unfragmented ions) were observed. It is not clear from the results whether these variations reflect structurally different ions or ions of different internal energies. The CA spectra of [C₆H₆]⁺˙ ions derived from charge exchange reactions between the benzene dication and the target gases He, Ne, Ar, Kr and Xe have also been recorded and, once again, very similar fragment abundance patterns were observed along with large variations in total CA fragment yields. Charge exchange efficiency measurements are reported for reactions between the benzene dication and the targets He, Ne, Ar, Kr, Xe and C₆H₆ (benzene) and also for the doubly charged ions derived from the linear C₆H₆ isomers. In the latter case Xe and benzene targets were used. The energetics and efficiency measurements for the former reactions suggest that for targets such as He and Ne the processes probably involve excited states of the doubly charged ions. The efficiencies measured for the latter reactions were distinctly different for the three C₆H₆ isomers and may indicate a strong dependence of charge exchange cross-section on doubly charged ion structure.     

Bowl-shaped hydrocarbons related to C60

Ab initio studies at the HF/6-31G* and B3LYP/6-31G* levels are reported for two bowl-shaped hydrocarbons related to C₆₀: C₃₀H₁₂ and C₃₆H₁₂, of C₃ and C_3v symmetry, respectively. The former has an approximate heat of formation of 211 kcal/mol. Bowl-to-bowl interconversion may occur through a planar (C_3h) form of ca. 64 kcal/mol greater energy having one imaginary vibrational frequency. The larger C₃₆H₁₂ bowl has a calculated ΔH°_f of 265 kcal/mol. Its HF/6-31G*, B3LYP/6-31G*, and MM3 bond lengths are in good agreement with a recent X-ray structure. Chemical shifts for both compounds calculated by the GIAO method are in good agreement with the measured NMR spectra. The observed ¹³C chemical shifts increase with the extent of pyramidalization. © 1998 John Wiley & Sons, Inc. J Comput Chem 19: 189–194, 1998     

Neutralization-reionization study of C6H6O isomers

Neutralization-reionization (⁺NR⁺) mass spectrometry is employed to examine the behavior of C₆H₆O isomers in the gas phase. Phenol and cyclohexa-2,4-dienone are found not to interconvert following neutralization with mercury of their corresponding cation radicals at 9.9 keV kinetic energy. A very low extent of isomerization is observed following collisional activation of fast C₆H₆O neutrals with helium. The ⁺NR⁺ and collisionally activated dissociation spectra, the latter obtained at unit mass resolution, are used to identify these [C₆H₆O]^{+ ˙} isomers. Hexa-1,3,5-trienal is found to cyclize spontaneously to cyclohexa-2,4-dienone during attempted pyrolytic preparation. The thermochemistry of these C₆H₆O molecules and cation radicals is discussed on the basis of experimental data and MNDO calculations.     

Investigation on stabilities and spectroscopy of C80O2 based on C80 (D5d) using density functional theory

The relative stabilities of the 17 possible isomers for C₈₀O₂ based on C₈₀ (D_5d) were studied using Becke three parameters plus Lee, Yang, and Parr's (B3LYP) method and 6‐31G (d) basis set in density functional theory. The most stable geometry of C₈₀O₂ was predicted to be 23,24,27,28‐C₈₀O₂ (A) with annulene‐like structures, where the additive bonds are those between two hexagons (6/6 bonds) near the equatorial belt of C₈₀ (D_5d). Electronic spectra of C₈₀O₂ isomers were calculated based on the optimized geometries using intermediate neglect of differential overlap (INDO) calculation. Compared with those of C₈₀ (D_5d), the first absorptions in the electronic spectra of C₈₀O₂ are blue‐shifted owing to the wide energy gaps. ¹³C nuclear magnetic resonance spectra and nucleus independent chemical shifts of the C₈₀O₂ isomers were computed at B3LYP/6‐31G level. The chemical shifts of the bridged carbon atoms in the epoxy structures of C₈₀O₂ compared with those of the bridged carbon atoms in the annulene‐like structures are changed upfield. Generally, the isomers with the annulene‐like structures of C₈₀O₂ are more aromatic than those with the epoxy structures. The addition of the oxygen atoms near the pole of C₈₀ (D_5d) is favorable to improving the aromaticities of C₈₀O₂. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2009