Infrared observation of OC-C2H2, OC-(C2H2)2 and their isotopologues

ABSTRACT

The fundamental band for the OC-C₂H₂ dimer and two combination bands involving the intermolecular bending modes ν₉ and ν₈ in the carbon monoxide CO stretch region are re-examined. Spectra are obtained using a pulsed supersonic slit jet expansion probed with a mode-hop free tuneable infrared quantum cascade laser. Analogous bands for OC-C₂D₂ and the fundamental for OC–DCCH as an impurity are also observed and analysed. A much weaker band in the same spectral region is assigned to a new mixed trimer, CO-(C₂H₂)₂. The trimer band is composed uniquely of a-type transitions, establishing that the CO monomer is nearly aligned with the a-inertial axis. The observed rotational constants agree well with ab initio calculations and a small inertial defect value indicates that the trimer is planar. The structure is a compromise between the T-shaped structure of free acetylene dimer and the linear geometry of free OC-C₂H_2. A similar band for the fully deuterated isotopologue CO-(C₂D₂)₂ confirms our assignment.     

The 13C2 and 12C13C Ballik-Ramsay system

The infrared spectrum of the b³Σ⁻ → a³Π Ballik-Ramsay system has been observed for both ¹³C₂ and ¹²C¹³C isotopic species using high-resolution Fourier transform spectroscopy. Twelve bands: 0 → 0, 1 → 0, 1 → 1, 2 → 0, 2 → 1, 3 → 1, 3 → 2, 4 → 2, 4 → 3, 5 → 2, 5 → 3, 6 → 3 of ¹³C₂ and seven bands: 0 → 0, 1 → 0, 1 → 1, 2 → 0, 2 → 1, 3 → 1, 3 → 2 of ¹²C¹³C were identified in the spectral range 3500–12 000 cm⁻¹. Perturbations in the b³Σ⁻ (v = 0, 1, 2, 3) levels were reduced and accurate perturbation parameters derived from the analysis. A comparison with ab initio calculated spin-orbit coupling constants is presented.     

The emission spectrum of 13C16O2 near 4.5 μm

The emission spectrum of ¹³C¹⁶O₂ near 4.5 μm, the ν₃ transition region, was measured in high resolution. The sequence 00v₃ → 00(v₃ ? 1) was measured to v₃ = 9, 01¹v₃ → 01¹(v₃ ? 1) to v₃ = 6, and 02²v₃ → 00²(v₃ ? 1) to v₃ = 3. Several bands involving Fermi resonant Σ state were also observed. The data were analyzed and spectroscopic constants were determined for all bands identified.     

The rotational spectrum of 13C2HD in the ground and excited bending states

The pure rotational spectrum of ¹³C₂HD was recorded in the range 100–700 GHz. Lines belonging to the ground vibrational state were observed from J^″ = 1 to J^″ = 11. Several absorption lines were also detected in the bending states v₄ = 1 (Π), v₅ = 1 (Π), v₄ = 2 (Σ⁺ and Δ), v₅ = 2 (Σ⁺ and Δ), v₄ = v₅ = 1 (Σ^?, Σ⁺ and Δ), v₄ = 3 (Π and Φ) and v₅ = 3 (Π and Φ). The transition frequencies measured in this work were fitted together with all the infrared lines available in the literature. The global fit allowed a very accurate determination of the vibrational, rotational and ?-type interaction parameters for the bending states of this molecule.     

Theoretical determination of the 1H NMR spectrum of ethanol

GIAO calculations of the ¹H NMR chemical shifts for ethanol at the SCF and DFT levels of theory are presented. The importance of molecular geometry and basis set is discussed. Vibrational correction to the hydroxyl proton chemical shift is also considered in calculations for the monomer of ethanol. The final theoretical results for the monomer obtained at the optimized DFT/B3LYP/6-311G(d,p) geometry with the 6-311G++ (d,p) basis set for NMR are in very good agreement with gas phase experimental data. For the liquid phase ethanol the hydrogen bonding effects are taken into account by performing calculations on various clusters of ethanol. It is shown that inaccuracy due to molecular geometry and basis set in the monomer of ethanol is magnified significantly in calculations for its clusters. In this context the structure of liquid ethanol as predicted recently by quantum cluster equilibrium (QCE) theory is discussed.     

High-resolution 1H and 13C NMR of solid 2-Aminobenzoic acid

Three crystalline modifications of 2-aminobenzoic acid (anthranilic acid) have been studied by ¹³C CP/MAS and ¹H CRAMPS NMR. The peaks are assigned and discussed in relation to (a) the neutral or zwitterionic nature of the molecules, (b) the crystal structures, known for two of the polymorphs, (c) residual (N,C) dipolar splittings, (d) hydrogen bonding and (e) dynamic exchange. The value of applying both types of spectroscopy to such studies is stressed.     

High-resolution Q-branches spectrum of C2H2 at 9366 and 9407 cm−1

The acetylene absorption spectrum in the Nd-laser range 9240–9520 cm^?1 has been recorded earlier (1), using a highly sensitive intracavity laser spectrometer. Two weak absorption perpendicular bands 2100⁰1¹ ← 0000⁰0⁰ (ν₀ = 9366.6 cm^?1) and 1200°3¹ ← 0000°0° (ν₀ = 9407.7 cm^?1) were studied and spectroscopic constants were obtained. However, the structure of the Q branches of these bands with J < 7 was unresolved because the resolution of the spectrometer was not very high.     

间接测量1H-13CT1和T2的方法

本文提出了间接测量¹H-¹³CT₁和T₂的新方法,这些方法能用于测量¹H谱不能很好分辨的分子。并对直接测量和间接测量结果进行分析比较。     

The C1 IIg-A1 IIu Emission Spectrum of 12C13C

A few bands of the C¹II_g -A¹II_u system of ¹²C¹³C molecule have been photographed and five of them have been rotationally analyzed. Molecular constants for v = 0, 1 and 2 in the C¹ II_g and in A¹II_u states have been obtained using a nonlinear least-squares procedure in which all analyzed bands were fitted simultaneosly.     

1H and 13C NMR Determination of 1-Naphtyl-Polymethoxylated Diphenylwiethanes

The complete structural analysis of 1-[(4-methoxyphenyl)-(3,4,5-trimethoxyphe- nyl)methyl]naphtalene 5a and 1-[(2,5-dimethoxyphenyl)-(3,4,5-trimethoxyphenyl) methyljnaphtalene 5b, prepared by alkylation of 1-[chloro-(3,4,5-trimethoxyphenyl) methyl]naphtalene without by-products such as benzofluorene 2, may be accurately determined by ¹H, ¹³C NMR and 2D NMR analysis.     

Quantum rotational scattering of H2 and its isotopologues with He

Quantum close-coupling computations of the rotational quenching of H₂ and its isotopologues due to He impact are performed using a highly accurate potential energy surface. State-to-state cross sections are obtained in a wide range of collision energies between 10^?5 cm^?1 and 10⁴ cm^?1, and the theoretical rate coefficients are reported for temperatures ranging from 10^?4 K to 3000 K. Compared with previous studies, the well depth of the potential adopted in this study is larger, leading to stronger resonance effects in the cross sections of He-HD. The accurate potential was employed to investigate the isotope effects of H₂ in detail. The cross-section resonances shift towards lower collision energies and become stronger with increasing reduced mass. The calculated cross sections and rate coefficients of H₂ and its isotopic variants in collisions with He are provided to study the energy transfer in these systems.     

一种热转印色素的1H、13C NMR研究

报道了一种热转印色带用黄染料的¹H、¹³C NMR , 应用¹H NMR、¹³C NMR、定量碳谱、DEPT、¹H-¹H COSY、HMQC、HMBC等确定了其在氘代氯仿中的分子结构, 并对全部谱峰进行了归属, 探索了黄染料在氘代氯仿中的结构对¹³C、¹H NMR谱图化学位移及谱峰裂分的影响.      

雪胆素C的1H和13C NMR化学位移完全归属

雪胆素C是一个雪胆素甲在碱性条件下，乙酰基转移产生的同分异构体. 文中报道了应用¹³C NMR-DEPT、¹H-¹H COSY, NOESY, ¹³C-¹H COSY等多种NMR技术，对雪胆素C的NMR碳氢化学位移完全指定.     

The13C/12C and 2H/1H Ratios of Trichloroethene,Tetrachloroethene and Their Metabolites

Abstract

Isotope ratios of technically and biologically produced halogenated hydrocarbons (HHC) are presented. Compared to the parent compounds, there is a significant enrichment of deuterium depending on the manner of production, whereas the carbon isotope ratio was only slightly influenced. Furthermore, there is nearly no alteration of the carbon isotope ratio due to biological degradation, so that the carbon fingerprint of the parent compounds is maintained in the metabolites. In contrast to this, the hydrogen isotope ratio of the metabolites reflects the ratio of the surrounding water. These results show that the isotopic fingerprint is a useful tool to distinguish between age, different charges of chemical dumping, and in addition to that, whether there is a contamination with technical products or residual metabolites.     

High resolution 2D 1H-13C correlation of cholesterol in model membrane

High resolution 2D NMR MAS spectra of liposomes, in particular 1H-13C chemical shifts correlations have been obtained on fluid lipid bilayers made of pure phospholipids for several years. We have investigated herein the possibility to obtain high resolution 2D MAS spectra of cholesterol embedded in membranes, i.e. on a rigid molecule whose dynamics is characterized mainly by axial diffusion without internal segmental mobility. The efficiency of various pulse sequences for heteronuclear HETCOR has been compared in terms of resolution, sensitivity and selectivity, using either cross polarization or INEPT for coherence transfer, and with or without MREV-8 homonuclear decoupling during t1. At moderately high spinning speed (9 kHz), a similar resolution is obtained in all cases (0.2 ppm for 1H(3,4), 0.15 ppm for 13C(3,4) cholesterol resonances), while sensitivity increases in the order: INEPT < CP(x4) < CP + MREV. At reduced spinning speed (5 kHz), the homonuclear dipolar coupling between the two geminal protons attached to C(4) gives rise to spinning sidebands from which one can estimate a H-H dipolar coupling of 10 kHz which is in good agreement with the known dynamics of cholesterol in membranes.     

2-环烷基苯腈的13C NMR研究

报道了7种新的2-环烷基苯腈的¹³C NMR谱.应用¹³C NMR等谱确定了这7种新化合物的分子结构,并对全部谱峰进行了归属,初步探讨了分子结构对¹³C NMR化学位移的影响.