Vibration–rotation variational calculations: precise results on HCN up to 25 000 cm−1

Variation calculations of the vibration–rotation energy levels of many isotopomers of HCN are reported, for J=0, 1, and 2, extending up to approximately 8 quanta of each of the stretching vibrations and 14 quanta of the bending mode. The force field, which is represented as a polynomial expansion in Morse coordinates for the bond stretches and even powers of the angle bend, has been refined by least squares to fit simultaneously all observed data on the Σ and Π state vibrational energies, and the Σ state rotational constants, for both HCN and DCN. The observed vibrational energies are fitted to roughly ±0.5 cm−1, and the rotational constants to roughly ±0.0001 cm−1. The force field has been used to predict the vibration rotation spectra of many isotopomers of HCN up to 25 000 cm−1. The results are consistent with the axis‐switching assignments of some weak overtone bands reported recently by Jonas, Yang, and Wodtke, and they also fit and provide the assignment for recent observations by Romanini and Lehmann of very weak absorption bands above 20 000 cm−1.

Vibration-rotation spectra of monofluoroacetylene: 1700 to 7500 cm−1

High-resolution vibration-rotation spectra of monofluoroacetylene are reported for many bands in the region 1700 to 7500 cm−1. The spectra were observed on Nicolet 7199 and Bruker IFS 120 Fourier spectrometers, with resolutions of about 0.06 and 0.003 cm−1, respectively. About 130 bands have been observed in this region, of which about 80 have been rotationally analyzed. The assignment of vibrational labels to the higher energy levels is complicated by the effects of strong Fermi resonances, and many weak localized rotational resonances are observed.

C–H local modes in cyclobutene. II. Laser photoacoustic studies 10 000–17 000 cm−1. Vibrational structure and C–H local mode dynamics

In part I of this study [Baggott, Clase, and Mills, Spectrochim. Acta Part A 42, 319 (1986)] we presented FTIR spectra of gas phase cyclobutene and modeled the v=1–3 stretching states of both olefinic and methylenic C–H bonds in terms of a local mode model. In this paper we present some improvements to our original model and make use of recently derived ‘‘x,K relations’’ to find the equivalent normal mode descriptions. The use of both the local mode and normal mode approaches to modeling the vibrational structure is described in some detail. We present evidence for Fermi resonance interactions between the methylenic C–H stretch overtones and ring C–C stretch vibrations, revealed in laser photoacoustic spectra in the v=4–6 region. An approximate model vibrational Hamiltonian is proposed to explain the observed structure and is used to calculate the dynamics of the C–H stretch local mode decay resulting from interaction with lower frequency ring modes. The implications of our experimental and theoretical studies for mode‐selective photochemistry are discussed briefly.

Carbon suboxide: the infrared spectrum from 1800 to 2600 cm-1

The infrared spectrum of carbon suboxide has been recorded from 1800 to 2600 cm−1 at a resolution of 0.003 cm−1. About 7% of the ca. 40 000 lines observed have been assigned and analyzed, belonging to 36 different bands. Most of these are associated with the fundamental ν3, at 2289.80 cm−1, and the combination band ν2 + ν4, at 2386.61 cm−1, each of which give rise to a system of sum bands, difference bands, and hot bands involving the low-wave-number fundamental ν7 at 18 cm−1. A few other tentative assignments are made. The bands have been analyzed for vibrational and rotational constants.

The high-resolution infrared spectrum of HOF near 2700 cm-1: the ground and 2v2 states

The a/b hybrid-type ν1 fundamental and 2ν2 overtone bands of HOF were investigated by FTIR spectroscopy with a resolution close to 0.008 cm−1. Improved ground state parameters of HOF were determined from a merge of more than 3000 ground state combination differences formed from ν1 and previously measured ν2 transitions with the reported pure rotational lines. Excited state parameters of the v2 = 2 state, ν0 = 2686.924 6(1) and χ22 = −9.942 4(1) cm−1, were determined employing Watson's A-reduced Hamiltonian up to sixth order in I′ representation. The 2ν2 state was found to be unperturbed, the excited state parameters being closely related to those of ν2.

Argon predissociation spectroscopy of the OH-center dot H2O and Cl-center dot H2O complexes in the 1000-1900 cm(-1) region: Intramolecular bending transitions and the search for the shared-proton fundamental in the hydroxide monohydrate

We present argon predissociation vibrational spectra of the OH-.H2O and Cl-.H2O complexes in the 1000-1900 cm(-1) energy range, far below the OH stretching region reported in previous studies. This extension allows us to explore the fundamental transitions of the intramolecular bending vibrations associated with the water molecule, as well as that of the shared proton inferred from previous assignments of overtones in the higher energy region. Although the water bending fundamental in the Cl-.H2O spectrum is in very good agreement with expectations, the OH-.H2O spectrum is quite different than anticipated, being dominated by a strong feature at 1090 cm(-1). New full-diniensionality calculations of the OH-.H2O vibrational level structure using diffusion Monte Carlo and the VSCF/CI methods indicate this band arises from excitation of the shared proton.

Highly excited vibrational states of HCN around 30 000 cm(-1)

This article describes the analysis and interpretation of rovibrational spectra involving highly excited vibrational states in the molecule of HCN. The spectra were obtained by means of the vibrationally mediated photodissociation technique. Analysis of the spectra revealed four bands with Sigma-Sigma structures that, once fitted, provided the energies and rotational constants of four new, highly excited vibrational states in the region of the potential energy surface near and above 30 000 cm(-1). All the states could be identified with the help of a state-of-the-art variational calculation. Together with the states already observed in previous works, eight highly excited states have so far been identified in this region. (c) 2006 American Institute of Physics.

Laboratory measurements of the water vapor continuum in the 1200–8000 cm−1 region between 293 K and 351 K

Laboratory Fourier transform spectroscopy of pure water vapor and water vapor mixed with air has been conducted between 1200 and 8000 cm−1 and at temperatures between 293 and 351 K with the purpose of detecting and characterizing the water vapor continuum. The spectral features of the continuum within the major water absorption bands are presented and compared where possible to those from previous experimental studies and to the commonly used MT_CKD and CKD models. It was observed that in the main, both models adequately capture the general spectral form of the continuum; however, there were a number of exceptions. Overall, there is no evidence to indicate that MT_CKD is an improvement upon the older CKD model in these spectral regions. There was generally good agreement between our results and those of other experimental investigators. The general mathematical forms of the self-continuum temperature dependence, given by both Roberts et al. (1976) and CKD/MT_CKD, fit well to the experimental continuum in these spectral regions. However, the range of temperatures over which we made measurements is not sufficient to discriminate between these two forms or to exclude the possibility of other forms of temperature dependence being more appropriate. At the same time, the actual parameters currently used in CKD/MT_CKD to describe the temperature dependence in many spectral regions cannot reproduce the observed strong spectral variation in the temperature dependence. It has not been possible to make definitive conclusions about the magnitude of the continuum absorption in the far wings of the absorption bands investigated here.

Systematic analysis of the Fourier transform spectrum of (CH3OH)-C-13 between 400 and 950 cm(-1)

We have investigated a high-resolution Fourier transform (FT) absorption spectrum of the (CH3OH)-C-13 isotopomer of methanol from 400 to 950 cm(-1) with the Ritz program. We present the assignments of 7160 transitions, 3021 of which belong to Asymmetry, and 4139 to E-symmetry. These transitions occur between states labeled by K quantum numbers up to 14, and by torsional quantum numbers n up to 4. The Ritz program evaluated the energies of the 4684 involved levels with an accuracy of the order of 10(-4) cm(-1). All of the assigned lines correspond to transitions involving torsionally excited levels within the ground small-amplitude vibrational state. (c) 2005 Elsevier B.V. All rights reserved.

RITZ ANALYSIS OF THE FOURIER SPECTRUM OF CH3OH BETWEEN 350 AND 950 CM(-1)

A new ''Ritz'' program has been used for revising and expanding the assignment of the Fourier transform infrared and far-infrared spectrum of CH3OH. This program evaluates the energy levels involved in the assigned transitions by the Rydberg-Ritz combination principle and can tackle such perturbations as Fermi-type resonances or Coriolis interactions. Up to now this program has evaluated the energies of 2768 levels belonging to A-type symmetry and 4133 levels belonging to E-type symmetry of CH3OH. Here we present the assignment of almost 9600 lines between 350 and 950 cm(-1). The Taylor expansion coefficients for evaluating the energies of the levels involved in the transitions are also given. All of the lines presented in this paper correspond to transitions involving torsionally excited levels within the ground vibrational state. (C) 1995 Academic Press, Inc.

Improved water vapour spectroscopy in the 4174-4300 cm-1 region and its impact on SCIAMACHY HDO/H2O measurements

The relative abundance of the heavy water isotopologue HDO provides a deeper insight into the atmospheric hydrological cycle. The SCanning Imaging Absorption spectroMeter for Atmospheric CartograpHY (SCIAMACHY) allows for global retrievals of the ratio HDO/H2O in the 2.3 micron wavelength range. However, the spectroscopy of water lines in this region remains a large source of uncertainty for these retrievals. We therefore evaluate and improve the water spectroscopy in the range 4174–4300 cm−1 and test if this reduces systematic uncertainties in the SCIAMACHY retrievals of HDO/H2O. We use a laboratory spectrum of water vapour to fit line intensity, air broadening and wavelength shift parameters. The improved spectroscopy is tested on a series of ground-based high resolution FTS spectra as well as on SCIAMACHY retrievals of H2O and the ratio HDO/H2O. We find that the improved spectroscopy leads to lower residuals in the FTS spectra compared to HITRAN 2008 and Jenouvrier et al. (2007) spectroscopy, and the retrievals become more robust against changes in the retrieval window. For both the FTS and SCIAMACHY measurements, the retrieved total H2O columns decrease by 2–4% and we find a negative shift of the HDO/H2O ratio, which for SCIAMACHY is partly compensated by changes in the retrieval setup and calibration software. The updated SCIAMACHY HDO/H2O product shows somewhat steeper latitudinal and temporal gradients and a steeper Rayleigh distillation curve, strengthening previous conclusions that current isotope-enabled general circulation models underestimate the variability in the near-surface HDO/H2O ratio.

Structural and optical properties of rare earth-doped (Ba(0.77)Ca(0.23))(1-x)(Sm, Nd, Pr, Yb)(x)TiO(3)

The structural, dielectric, and vibrational properties of pure and rare earth (RE)-doped Ba(0.77) Ca(0.23)TiO(3) (BCT23; RE = Nd, Sm, Pr, Yb) ceramics obtained via solid-state reaction were investigated. The pure and RE-doped BCT23 ceramics sintered at 1450 degrees C in air for 4 h showed a dense microstructure in all ceramics. The use of RE ions as dopants introduced lattice-parameter changes that manifested in the reduction of the volume of the unit cell. RE-doped BCT23 samples exhibit a more homogenous microstructure due to the absence of a Ti-rich phase in the grain boundaries as demonstrated by scanning electron microscopy imaging. The incorporation of REs led to perturbations of the local symmetry of TiO(6) octahedra and the creation of a new Raman mode. The results of Raman scattering measurements indicated that the Curie temperature of the ferroelectric phase transition depends on the RE ion and ion content, with the Curie temperature shifting toward lower values as the RE content increases, with the exception of Yb(3+) doping, which did not affect the ferroelectric phase transition temperature. The phase transition behavior is explained using the standard soft mode model. Electronic paramagnetic resonance measurements showed the existence of Ti vacancies in the structure of RE-doped BCT23. Defects are created via charge compensation mechanisms due to the incorporation of elements with a different valence state relative to the ions of the pure BCT23 host. It is concluded that the Ti vacancies are responsible for the activation of the Raman mode at 840 cm(-1), which is in agreement with lattice dynamics calculations. (c) 2011 American Institute of Physics. [doi:10.1063/1.3594710]

Design of 1D and 2D molecule-based magnets with the ligand 4,5-dimethyl-1,2-phenylenebis(oxamato)

Three new bimetallic oxamato-based magnets with the proligand 4,5-dimethyl-1,2-phenylenebis-(oxamato) (dmopba) were synthesized using water or dimethylsulfoxide (DMSO) as solvents. Single crystal X-ray diffraction provided structures for two of them: [MnCu(dmopba)(H(2)O)(3)]n center dot 4nH(2)O (1) and [MnCu(dmopba)(DMSO)(3)](n center dot)nDMSO (2). The crystalline structures for both 1 and 2 consist of linearly ordered oxamato-bridged Mn(II)Cu(II) bimetallic chains. The magnetic characterization revealed a typical behaviour of ferrimagnetic chains for 1 and 2. Least-squares fits of the experimental magnetic data performed in the 300-20 K temperature range led to J(MnCu) = -27.9 cm(-1), g(Cu) = 2.09 and g(Mn) = 1.98 for 1 and J(MnCu) = -30.5 cm(-1), g(Cu) = 2.09 and g(Mn) = 2.02 for 2 (H = -J(MnCu)Sigma S(Mn, i)(S(Cu, i) + S(Cu, i-1))). The two-dimensional ferrimagnetic system [Me(4)N](2n){Co(2)[Cu(dmopba)](3)}center dot 4nDMSO center dot nH(2)O (3) was prepared by reaction of Co(II) ions and an excess of [Cu(dmopba)](2-) in DMSO. The study of the temperature dependence of the magnetic susceptibility as well as the temperature and field dependences of the magnetization revealed a cluster glass-like behaviour for 3.

XSophe-Sophe-XeprView (R). A computer simulation software suite (v. 1.1.3) for the analysis of continuous wave EPR spectra

The XSophe-Sophe-XeprView((R)) computer simulation software suite enables scientists to easily determine spin Hamiltonian parameters from isotropic, randomly oriented and single crystal continuous wave electron paramagnetic resonance (CW EPR) spectra from radicals and isolated paramagnetic metal ion centers or clusters found in metalloproteins, chemical systems and materials science. XSophe provides an X-windows graphical user interface to the Sophe programme and allows: creation of multiple input files, local and remote execution of Sophe, the display of sophelog (output from Sophe) and input parameters/files. Sophe is a sophisticated computer simulation software programme employing a number of innovative technologies including; the Sydney OPera HousE (SOPHE) partition and interpolation schemes, a field segmentation algorithm, the mosaic misorientation linewidth model, parallelization and spectral optimisation. In conjunction with the SOPHE partition scheme and the field segmentation algorithm, the SOPHE interpolation scheme and the mosaic misorientation linewidth model greatly increase the speed of simulations for most spin systems. Employing brute force matrix diagonalization in the simulation of an EPR spectrum from a high spin Cr(III) complex with the spin Hamiltonian parameters g(e) = 2.00, D = 0.10 cm(-1), E/D = 0.25, A(x) = 120.0, A(y) = 120.0, A(z) = 240.0 x 10(-4) cm(-1) requires a SOPHE grid size of N = 400 (to produce a good signal to noise ratio) and takes 229.47 s. In contrast the use of either the SOPHE interpolation scheme or the mosaic misorientation linewidth model requires a SOPHE grid size of only N = 18 and takes 44.08 and 0.79 s, respectively. Results from Sophe are transferred via the Common Object Request Broker Architecture (CORBA) to XSophe and subsequently to XeprView((R)) where the simulated CW EPR spectra (1D and 2D) can be compared to the experimental spectra. Energy level diagrams, transition roadmaps and transition surfaces aid the interpretation of complicated randomly oriented CW EPR spectra and can be viewed with a web browser and an OpenInventor scene graph viewer.