Microwave and infrared spectroscopy of the CH4—OCS complex

Pulsed molecular beam spectra of the CH₄-OCS complex have been recorded using both a molecular beam infrared diode laser and a Fourier transform microwave spectrometer. Analysis of the spectrum yields a near T shape structure with a centre of mass separation of 3.83 Å and a CH₄ centre of mass-OCS centre of mass-oxygen angle of 73°. Splittings attributed to the internal rotations of methane within the complex have been observed in the microwave spectrum. The rotational constants of the complex for the A and T librational states of CH₄ were determined. The differences (T-A) in the rotational constants were ΔA = 0.35, ΔB = ?1.60 and ΔC = ?1.85 kHz.     

Insights into copper coordination in the EcoRI–DNA complex by ESR spectroscopy

The EcoRI restriction endonuclease requires one divalent metal ion in each of two symmetrical and identical catalytic sites to catalyse double-strand DNA cleavage. Recently, we showed that Cu²⁺ binds outside the catalytic sites to a pair of new sites at H114 in each sub-unit, and inhibits Mg²⁺-catalysed DNA cleavage. In order to provide more detailed structural information on this new metal ion binding site, we performed W-band (～94 GHz) and X-band (～9.5 GHz) electron spin resonance spectroscopic measurements on the EcoRI–DNA–(Cu²⁺)₂ complex. Cu²⁺ binding results in two distinct components with different g_zz and A_zz values. X-band electron spin echo envelope modulation results indicate that both components arise from a Cu²⁺ coordinated to histidine. This observation is further confirmed by the hyperfine sub-level correlation results. W-band electron nuclear double resonance spectra provide evidence for equatorial coordination of water molecules to the Cu²⁺ ions.     

Isolation of fe charge states by ion implantation and their study by mössbauer spectroscopy

Matrix isolation of impurity atoms in a frozen rare-gas lattice is a well-known technique for the study of atoms in quasi-free states. The usual procedure consists of co-evaporating these atoms together with the matrix atoms and depositing them simultaneously on a cold substrate. Subsequently, the frozen samples can be studied by optical spectroscopy or, as has been proved more recently, by Mössbauer spectroscopy.

The technical limitations of the co-evaporation procedure narrow the application range of this method. We have therefore tried to develop the ion implantation technique as a suitable alternative to the co-evaporation. Ion implantation does not put any limitation on the species and the concentration of the isolated atoms; moreover, it is particularly suited for the isolation of radioactive impurities, which may be investigated by Mossbauer spectroscopy.

In a first series of experiments, we have implanted ⁵⁷Co into a frozen Xe matrix, hereby producing isolated Fe⁺ and Fe⁰ states by the electron capture decay of the implanted nuclei.¹ A second experiment was devoted to the study of ⁵⁷Fe implanted in solid O₂.² Due to the high reactivity of oxygen, it would have been impossible to produce this sample by co-evaoporation. Mössbauer data show some evidence that in this case Fe⁶⁺ states have been produced. The results of these experiments will be discussed and further perspectives will be sketched.     

Effective orientation of water in 1,4-dioxane···water: the rotational spectrum of the H2 17O isotopologue

The measurements of the rotational spectrum of 1,4-dioxane-water complex, performed by pulsed jet Fourier transform microwave spectroscopy, have been extended to the 7–18.5 GHz frequency region and to two additional isotopologues, 1,4-dioxane···H₂ ¹⁷O and 1,4-dioxane···HOD. The effective orientation of water in the complex has been obtained from the ¹⁷O quadrupole coupling constants.     

Monitoring by Mössbauer spectroscopy the thermal reduction of hematite into magnetite: the surface effect and charge disproportionality in iron oxide nanoparticles

Nanoparticles of magnetite Fe₃O₄ were synthesized by thermal reduction of hematite α-Fe₂O₃ powder in the presence of high boiling point solvent. The structural transformations and magnetic properties of the obtained nanoparticles were investigated by the ⁵⁷Fe Mössbauer spectroscopy, X-ray diffraction, and magnetic measurements. The content of hematite and magnetite phases was evaluated at each step of the chemical and thermal treatment of the product. An increase of saturation magnetization with the reaction time correlates with an increase of concentration of magnetite in the samples. The electron hoping between Fe^2?+? and Fe^3?+? ions in the octahedral sites of the magnetite nanoparticles and Verwey phase transition were investigated. It was established that not all iron ions in the octahedral sites participated in electron hoping Fe^2?+????Fe^3?+? above the Verwey temperature T _V, and the charge distribution could be expressed as $\big( {{\rm Fe}^{3+}}\big)_{{\rm tet}} \big[ {{\rm Fe}_{1.85}^{2.5+} {\rm Fe}_{0.15}^{3+} }\big]_{{\rm oct}} {\rm O}_4$ .     

The mutual relationship between H-bonding and π-stacking interactions: the estimation of individual binding energies in the phenylalanine:G ··· C ternary complex

The mutual relationship between stacked interaction and the individual hydrogen bonds in the phenylalanine:guanine?···?cytosine (Ph:G-C) and phenylalanine:cytosine?···?guanine (Ph:C-G) complexes have been studied at the MPWB1K/6-311++G** and M05-2X/cc-pVDZ levels of theory. The interplay of π-stacking and H-bonding results in the weakening of both interactions. The effect of π-stacking on the geometries and individual hydrogen bond (HB) energies of guanine–cytosine (G-C) base pair have been investigated using electron densities calculated by the atoms in molecules (AIM) method at the hydrogen bond critical points (BCP). The results of AIM analysis are in good agreement with the calculated individual hydrogen bond energies. The π-stacking interactions strengths the HB1 and weakens HB2 and HB3 in the Ph:G-C complexes, while the opposite is true in the Ph:C-G complex. With the increase in the distance between phenylalanine ring and the groups involved in H-bond interactions the change in the H-bond energy increases and the changes in the individual H-bond and π-stacking energies decrease in the ternary complexes.     

Determination of the Co valence in bilayer hydrated superconducting NaxCoO2 · yH2O by soft x-ray absorption spectroscopy

We addressed the so-far unresolved issue concerning the Co valence in the superconducting bilayer hydrated Na(x)CoO(2) · yH(2)O (x～0.35, y～1.3) using soft x-ray absorption spectroscopy at the Co-L(2,3) and O-K edges. We find that the valence state of the Co lies in a narrow range from +3.3 to +3.4 for all studied Na(x)CoO(2) · yH(2)O samples and their deuterated analogue with T(c)'s ranging from 3.8 to 4.7 K. These valence values are far from the often claimed +3.7, the number based on the Na content only. We propose to modify the phase diagram accordingly, where the basic electronic structure of the superconducting phase is very close to that of the Na(0.7)CoO(2) system, suggesting that the presence of in-plane spin fluctuations could play an important role for the superconductivity.     

Theoretical studies of three-dimensional potential energy surfaces using neural networks and rotational spectra of the Ar–N2 complex

ABSTRACT

A new three-dimensional potential energy surface (PES) of the Ar–N₂ van der Waals complex is constructed using the neural network method based on ab initio data points at the CCSD(T) level. The aug-cc-pVQZ basis set is employed for all atoms with midbond functions. The vibrationally averaged PES V₀₀ is characterised by a global T-shaped minimum which occurs at R = 3.715 Å, θ = 90.0° with a well depth of 98.779 cm^?1. Based on our three-dimensional PES, bound-state calculations are performed for three isotopomers of Ar–¹⁴N₂, Ar–¹⁵N₂, and Ar–¹⁴N¹⁵N, and several intermolecular vibrational states are assigned by analysing the wavefunctions. Moreover, the averaged structural parameters are calculated and the pure rotational transition frequencies with J = 0--6 are predicted. The spectroscopic constants are determined by fitting the rotational energy levels. The theoretical results are in good agreement with experimental data and this work gives more accurate results than those determined previously for the Ar–N₂ complex.     

Translational and rotational mode coupling in disordered ferroelectric KTa1−xNbxO3 studied by Raman spectroscopy

The coupling of translational modes to the reorientational motion is an essential property of systems with internal orientational degrees of freedom. Due to their high complexity most of those systems (molecular crystals, glasses, etc.) present a major puzzle for scientists. In this paper we analyze the Raman scattering of a relatively simple ferroelectric system, KTa_1−xNb_xO₃, which may serve as a model for more complicated cases. We show the presence of a strong coupling between translational and reorientational motion in the crystal. Our data suggest that this coupling is the main reason for the depolarized component of the second-order Raman spectra and that it is also responsible for the frequency decrease (softening) of the transverse acoustic mode down to the third of three transitions, below which reorientational motion is no longer allowed.     

Absolute line intensities in the ν1 + 3ν3 band of 12C2H2 by laser photoacoustic spectroscopy and Fourier transform spectroscopy

Line intensities and self-broadening coefficients in the ν₁ + 3ν₃ band of ¹²C₂H₂ near 0.8 μm at room temperature were measured by means of both laser photoacoustic and Fourier transform spectroscopy. An experimental protocol has been developed to obtain absolute intensities from the photoacoustic measurements. Namely, the spectrometer was calibrated using water vapour line intensities available in Hitran 1996 [L. S. Rothman et al. (1998) J. quant. Spectrosc. Radiat. Transfer, 60, 665–710]. These photoacoustic line intensities were found to be on average 5% higher than corresponding measurements performed using Fourier transform spectroscopy, the accuracy of the latter being estimated to better than 4%. The accuracy of the photoacoustic intensities is discussed. Previous results from the literature [F. Herregodts, D. Hurtmans, J. Vander Auwera, and M. Herman (1999) J. chem. Phys., 111, 7954—7960] are revised.     

Redox reaction of μ−O in water determined by the chemical shift

The chemical shift of ^–O in water, ice and in aqueous hydrogen peroxide (H₂O₂) was examined using ^–O resonance. Two distinct signals are obtained in water and ice. Using ⁺ resonance signal as a standard, the observed shiftsg are –7.0×10^–4 (signal A) and –12.1×10^–4 (signal B) respectively. The intensity of the two fractions are almost equivalent in water; however, in ice, the intensity of signal B decreases with increase of signal A. After the addition of hydrogen peroxide to the water signal B disappears, A increases, and the total amplitude is increased.     

Calculation of the binding energy and of the parameters of low-energy scattering in the Λnp system

The cluster-reduction method is used to solve the differential Faddeev equations for S=1/2, T=0 and S=3/2, T=0 spin-isospin states of the Λnp system in the s-wave approximation. The NN interaction is simulated on the basis of the MT I–III potential model, and the ΛN potential is set to V _ΛN =V _NN /2. This simple option makes it possible to reproduce faithfully the binding energy of the hypertriton _Λ ³ H. The doublet and quadruplet Λd scattering lengths and the low-energy phase shifts are calculated. It is shown that the effective-range approximation is applicable to the cases of doublet and quadruplet scattering.     

A hydrogen bonded complex C2H2…HBr isolated and characterized in the gas phase using pulsed-jet,Fourier transform microwave spectroscopy

A complex formed from ethyne and hydrogen bromide has been isolated and characterized by using a fast-mixing nozzle in conjunction with a pulsed-jet, Fourier transform microwave spectrometer. Any possible chemical reaction between the two components when mixed in the usual way was thereby precluded. The rotational constants A, B and C, the quartic centrifugal distortion constants δ_J, δ_Jk and δ_J and the Br nuclear hyperfine coupling constants X_aa and X_bb—X_cc (nuclear quadrupole) and M_bb (spin-rotation) were determined for each of the five isotopomers C₂H₂…H⁷⁹Br, C₂H₂…H⁸¹ Br, C₂H₂…D⁷⁹Br, C₂H₂…D⁸¹Br and C₂D₂…H⁷⁹Br. Interpretations of the spectroscopic constants show that the complex is planar and T shaped in the equilibrium conformation, with HCCH internuclear axis forming the cross of the T and the HBr internuclear axis lying along the C₂ axis of C₂H₂. The H of HBr is closer to the centre (?) of the π bond of ethyne, and therefore HBr is involved in a hydrogen bond to the π system, in which the distance of H from ? is r (?…H) = 2.469(1) A. The intermolecular stretching force constant is estimated as kσ = 5.38(2) Nm^?1 for the species involving a hydrogen bond (C₂H₂…H⁷⁹Br, C₂H₂…H⁸¹Br and C₂D₂…H⁷⁹Br) while this quantity increases to kσ = 5.68(2)Nm^?1 for those complexes bound through a deuterium bond (C₂H₂…D⁷⁹Br and C₂H₂…D⁷⁹Br). The opportunity is taken to consider similarities in the properties of complexes within the two series B…HBr and B…HC1 for a range of Lewis bases B, including B = C₂H₂. Some family relationships are identified in the two series.     

High-precision laser and RF spectroscopy of the spin-rotation and HFS interactions in the X2Σ+ and B2Σ+ states of LaO

The spin-rotation and hyperfine interactions in the X²Σ⁺ and B²Σ⁺ electronic states of ¹³⁹La¹⁶O have been studied using Doppler-free laser-induced fluorescence and molecular-beam laser-rf double resonance. Observations were made for several values of v and many values of N, allowing evaluation of the principal interaction strengths and their N and v dependences for both the X and B states. The results are compared with earlier results for the isoelectronic system ¹³⁷Ba¹⁹F.     

Study of the levels in 174Lu by (p, 3nγ) spectroscopy

The nuclear levels in ¹⁷⁴Lu were investigated by means of ¹⁷⁶Yb(p, 3nγ) reaction spectroscopy. Standard germanium detector techniques as well as an on-line curved crystal spectrometer were used. Six well-developed rotational bands are observed. These results confirm and extend the scheme previously obtained by direct reactions. The presented data document a study on the anomalous g-factors of the 142 d isomeric band.