Vibrational spectra and structure of 4-cyano-4′-pentalkoxybiphenyl in different physical states

The polymorphism, conformation mobility and structure of 4-cyano-4′-pentalkoxybiphenyl (5OCB) in different physical states are studied by IR spectroscopy. The spectra were measured in the frequency range 400–4000 cm⁻¹ at temperatures from 300 to 350 K. The IR spectra of 5OCB are modeled using the concept of conformational mobility of these molecules. An analysis of the experimental and theoretical spectra reveals absorption bands whose spectroscopic parameters are sensitive to variations of temperature (experiment) and conformation (theory); a relationship between these changes is established. It is concluded that the polymorphism of 5OCB is of conformation type. In the solid crystalline state, 5OCB molecules have conformations with a planar biphenyl fragment; the angle of orientation of the plane of the carbon framework of the alkyl radical relative to the biphenyl fragment decreases as the temperature increases from 35° in the solid crystalline state to 10° in the liquid crystalline and isotropic liquid states. In both of these states the biphenyl fragment becomes nonplanar. The angle between the phenyl rings is up to 30°. Saratov State University. Institute of Physics, Ukrainian Academy of Sciences. Samarkand State University. Translated fromZhurnal Strukturnoi Khimii, Vol. 39, No. 1, pp. 55–60, January–February, 1998. This work was supported by RFFR grant No. 97-03-32175a.     

Vibrational spectrum of cyclic TiC3 in solid Ar

The Fourier transform infrared spectrum of TiC3 was observed by trapping the vapor produced during dual Nd:YAG laser ablation of Ti and C rods in solid Ar at approximately 9 K. Measurements of frequencies and 13C isotopic shifts have enabled the identification of the fanlike (C(2v)) isomer of TiC3 with fundamental vibrations nu3(a1) = 624.3 and nu5(b2) = 1484.2 cm(-1). A third fundamental nu4(b1) has been tentatively identified at 573.8 cm(-1). The results are in good agreement with the predictions of density functional theory calculations at the B3LYP6-311G(3df,3pd) level. The observed C(2v) structure and the observed nu3 metal-carbon stretching mode are also consistent with earlier results from photoelectron spectroscopy.     

Vibrational energy levels for CH4 from an ab initio potential

Many areas of astronomy and astrophysics require an accurate high temperature spectrum of methane (CH4). The goal of the present research is to determine an accurate ab initio potential energy surface (PES) for CH4. As a first step towards this goal, we have determined a PES including up to octic terms. We compare our results with experiment and to a PES based on a quartic expansion. Our octic PES gives good agreement with experiment for all levels, while the quartic PES only for the lower levels.     

Reevaluation of term isotope shifts of low even levels of 4f86s2 configuration and high odd-parity levels of neutral gadolinium atoms

Isotope shift ΔT(¹⁵⁶Gd–¹⁶⁰Gd) of the even-parity energy levels of 4f⁸6s² and 4f⁷6s²6p configurations of neutral gadolinium atoms (Gd I) have been reevaluated using the level isotope shift (ΔT) of two odd-parity levels reported recently. Earlier the isotope shifts of these even-parity energy levels were evaluated using empirical relation. Our extensive isotope shift data has been used for the reevaluation of ΔT values of these low even-parity energy levels which have been utilised for revision of the ΔT values of high-lying odd-parity energy levels of Gd I.     

Lifetime measurement of some levels belonging to 3p 4 4p configuration of Ar II

High frequency deflection technique with delayed coincidence single photon counting arrangement has been used to measure the lifetimes of some excited states of argon II. The measurements have been performed under conditions where pressure-dependent effect is negligible. The instrumental response function has been obtained directly and the measured decay curves have been deconvoluted using this response function to yield the lifetimes of the levels concerned.     

Vibrational density of states and Lindemann melting law

We examine the Lindemann melting law at different pressures using the vibrational density of states (DOS), equilibrium melting curve, and Lindemann parameter delta(L) (fractional root-mean-squared displacement, rmsd, at equilibrium melting) calculated independently from molecular dynamics simulations of the Lennard-Jones system. The DOS is obtained using spectra analysis of atomic velocities and accounts for anharmonicity. The increase of delta(L) with pressure is non-negligible: delta(L) is about 0.116 and 0.145 at ambient and extreme pressures, respectively. If the component of rmsd normal to a reflecting plane as in the Debye-Waller-factor-type measurements using x rays is adopted for delta(L), these values are about 0.067 (+/-0.002) and 0.084 (+/-0.003), and are comparable with experimental and calculated values for face-centered-cubic elements. We find that the Lindemann relation holds accurately at ambient and high pressures. The non-negligible pressure dependence of delta(L) suggests that caution should be exerted in applying the Lindemann law to obtaining the high pressure melting curve anchored at ambient pressure.     

Ar2H+ 分子振动光谱的理论计算

基于近期由本组提供的Ar2H+分子的基态势能面,应用含时波包演化方法,计算了总角动量J=0时的振动光谱,并对其中的一些谱峰进行了指认.与现有的ab initio结果进行比较,这个新势能面包含了关于Ar2H+基态的比较正确的信息.     

Vibrational dynamics of excited electronic states of molecular iodine

Femtosecond degenerate four-wave-mixing spectroscopy following an initial pump laser pulse was used to observe the wave packet dynamics in excited electronic states of gas phase iodine. The focus of the investigation was on the ion pair states belonging to the first tier dissociating into the two ions I-(1S) + I+(3P2). By a proper choice of the wavelengths of the initial pump and degenerate four-wave-mixing pulses, we were able to observe the vibrational dynamics of the B (3)Pi(u) (+) state of molecular iodine as well as the ion pair states accessible from there by a one-photon transition. The method proves to be a valuable tool for exploring higher lying states that cannot be directly accessed from the ground state due to selection rule exclusion or unfavorable Franck-Condon overlap.     

Vibrational relaxtion in excited electronic states of aromatic hydrocarbons

Time-resolved experiments are reported Showing kinetic evidence for vibrational relaxation of electronically excited molecules in solution at room temperature. The experiments involve higher electronic states of 3,4,9,10-dibenzpyrene. Data are consistent with slow vibrational relaxation (≈ 15 ps), similar to that for ground state species.     

Vibrational relaxation in the excited states of large molecules

Theoretical analysis of the time-dependent triplet-triplet absorption spectrum of anthracene is carried out in terms of the Huang-Rhys spectral function which describes the absorption of molecules thermally equilibrated, due to fast intramolecular processes, at some effective temperature T^*(t) depending on time because of the collisions with the buffer-gas molecules. The close match between the theoretical spectra and the spectra observed by Porter et al. is demonstrated.     

复合物C6H5CH3…Ar分子间的外部振动频率

利用双光子共振电离光谱和飞行时间质谱技术在超声分子束中观察到C6H5CH3…Ar的振动光谱.借助同位素光谱效应、内转动能级和分子间振动能级的理论计算,合理地归属了涉及CH3转动和Ar原子振动的光谱,并由此获得复合物分子间各种模式的振动频率.     

Vibrational spectra and vibrational states of simple gas-phase hydrogen-bonded dimers

The article aims to outline the growth of evidence and ideas about infrared band broadening for simple, gaseous, moderately strong, hydrogen bonded dimers B…HA, to draw attention to areas in need of further development and to collect together experimental information available at the present time about vibrational states associated with such dimers. The band associated with the modified HA stretching mode, ν_s, is observed for several dimers not only to be broad, but to have sub-band structure, which is satisfactorily interpreted as arising from combination bands of ν_s with the low frequency stretch-mode ν_σ, giving a progression ν_s ± nν_σ as a result of strong anharmonic coupling. For weaker dimers with lower values of ν_σ the sub-band structure is less evident, and may appear only as shoulders, while for still weaker dimers, the sub-bands may be merged into a featureless broad band. A major factor contributing to the breadth of the individual sub-bands in the band structure is the presence of hot-bands, especially a long series based on successive excited states of the low-frequency bending mode ν_β. A link is indicated with the interpretation of band-broadening for moderately strong hydrogen-bonded complexes in the liquid state. The anharmonic coupling of ν_s and ν_σ is again a central feature but there is a new factor, namely the coupling of ν_σ through a fluctuating potential with the surroundings, which has the result that the ν_s mode rapidly loses phase coherence resulting in a broad structureless band.     

Vibrational spectra of germanium-carbon clusters in solid Ar: identification of the nu4(sigma(u)) mode of linear GeC5Ge

The linear GeC(5)Ge cluster has been detected in Fourier transform infrared spectra observed when the products from the dual laser evaporation of carbon and germanium rods were trapped in solid Ar at approximately 10 K. Comparison of (13)C isotopic shift measurements with the predictions of density functional theory calculations at the B3LYP/cc-pVDZ level confirms the identification of the nu(4)(sigma(u)) mode of GeC(5)Ge at 2158.0 cm(-1).     

Group IB organometallic chemistry: XXIX. Synthetic and structural aspects of polynuclear arylcopperlithium compounds Ar4Cu2Li2 (“arylcuprates”) and interaggregate exchange phenomena in Ar4Cu4/Ar4Li4/Ar4Cu2Li2 systems

The thermally stable arylmetal-IB-lithium compounds (2-Me₂NCHZC₆H₄)₄M₂Li₂ (M = Cu, Ag or Au; Z = H or Me) and (2-Me₂NC₆H₄)₄M₂Li₂ have been prepared by a $\text{2}\text{1}$ molar reaction of the aryllithium compounds with the corresponding metal-IB halide (Cu or Ag) or metal-lB halide phosphine complex (BrAuPPh₃). These tetranuclear complexes were also made by an interaggregate exchange reaction of the pure arylmetal-IB clusters with the aryllithium compound.The structure of these compounds in solution consists of aryl groups bridging one metal-lB and one lithium atom of a trans M₂Li₂ core. The four built-in ligands coordinate to lithium resulting in two-coordination at M and four-coordination at Li. These conclusions were based on ¹H and ¹³C NMR spectroscopic data (J(AgC(1)), J(LiC(1)) of solutions of these tetranuclear compounds as well as on the ¹⁹⁷Au Mössbauer data of solid (2-Me₂NC₆H₄)₄Au₂Li₂ (IS 5.65 mm/s and QS 12.01 mm/s).The interaggregate exchange between the tetranuclear species is discussed in terms of an associative mechanism involving formation of an octanuclear intermediate in which the aryl groups can migrate via (3c-2e)edge-(2c-2e)corner(3c-2e)edge movements without M₂Ar bond cleavage.Some aspects of the organic reactions in which organocuprates are involved as intermediates are discussed in terms of the novel structural information.     

Vibrational spectra of pyrazole in various aggregate states and their interpretation

The selection of the fundamental frequencies of pyrazole and the assignment of them to various types of vibrations were made on the basis of a comparison of the IR and Raman spectra of pyrazole and some of its isotopically substituted derivatives in various aggregate states and in the form of complexes with CdCl₂. The assignment was confirmed by prior calculation of the frequencies and forms of the vibrations of pyrazole.     

Vibrational energy levels of ozone up to dissociation revisited

Two recent papers presented calculations of the highly excited vibrational states of ozone. The nature and energies of these states may hold the key to the anomalous isotopic distribution of ozone in the atmosphere. Even though the same potential energy surface of Babikov et al. was used in both calculations, the number of bound van der Waals states reported below dissociation differed significantly. In order to resolve the issue we present here the results of an independent computation of all the bound vibrational states of (16)O(16)O(16)O and (16)O(16)O(18)O up to dissociation. Our methods differ from both earlier calculations since we use hyperspherical coordinates and a direct product discrete variable representation of the Hamiltonian. The results of present work support the existence of several van der Waals states for J=0 on this potential energy surface.