Morse Franck-Condon Factors and R-Centroids for Some Lyman Bands of H2, HD and D2

Using new rotational and vibrational constants, Morse Franck-Condon factors and r-centroids are computed for 108 Lyman bands of astrophysical importance H₂, HD and D₂ molecules. Experimental oscillator strengths conjoint with Morse Franck-Condon Factors for six Lyman bands of molecular hydrogen yield radiative lifetimes for v = 0–5 levels of the B 1σ_u ⁺ state that are inconsistent with the experimental lifetime measurements. The limitation of analytic Morse function in the region of small internuclear separation for the B 1σ_u ⁺ state of H₂ is discussed. The r-centroids (r_v′v″) are found to increase with frequencies of the Lyman bands of H₂, HD and D₂. For a sequence, Δr = r_{v′+1,v″+1} - r_v′v″ is constant. A comparison of r_v′v″ values of the Lyman bands shows that r_v′vv″ of the band (v′v″) increases in going from H₂ to D₂.     

Rotational spectra of mono-substituted asymmetric C6H6-H2O dimers

This paper reports the assignment of the rotational spectra of the m = 0 and 1 states of ¹³CC₅H₆-H₂O and C₆H₅D-H₂O dimers. The m = 1 progression was not identified or assigned for both ¹³CC₅H₆-H₂O and C₆H₅D-H₂O in the earlier work, though for the symmetric isotopomers (C₆H₆-H₂O/D₂O/H₂¹⁸O), they were identified [H.S. Gutowsky, T. Emilsson, E. Arunan, J. Chem. Phys. 99 (1993) 4883]. The m = 1 transitions for ¹³CC₅H₆-H₂O and C₆H₅D-H₂O were split into two, unlike that of the parent C₆H₆-H₂O isotopomer. The splitting varied, somewhat randomly, with quantum numbers J and K. The m = 0 lines of ¹³CC₅H₆-H₂O had significant overlap with the m = 1 lines of the parent isotopomer, clouding proper assignment, and leading to an rms deviation of about 200 kHz in the earlier work. The general semi-rigid molecular Hamiltonian coupled to an internal rotor, described recently by Duan et al. [Y.B. Duan, H.M. Zhang, K. Takagi, J. Chem. Phys. 104 (1996) 3914], is used in this work to assign both m = 0 and 1 states of ¹³CC₅H₆-H₂O and C₆H₅D-H₂O dimers. Consequently, the m = 0 fits for ¹³CC₅H₆-H₂O/D₂O have an rms deviation of only 4/7 kHz, comparable to experimental uncertainties. The fits for m = 1 transitions for ¹³CC₅H₆-H₂O and C₆H₅D-H₂O dimers have an rms deviation of about 200 kHz. However, it is of the same order of magnitude as that of the m = 1 state of the parent C₆H₆-H₂O dimer. The A rotational constants determined from the m = 0 fits for both ¹³CC₅H₆-H₂O and ¹³CC₅H₆-D₂O isotopomers are identical and very close to the C rotational constant for ¹³CC₅H₆. This provides a direct experimental determination for the C rotational constant of ¹³CC₅H₆, which has a negligible dipole moment.     

Bestimmung der Atomspinkorrelationszeiten der Fe3+-Ionen in FeNH4(SO4)2·12 H2O mit Hilfe des Mössbauereffektes

The Mössbauer effect studies of⁵⁷Fe in the paramagnetic salt FeNH₄(SO₄)₂·12 H₂O reported byObenshain et al. were extended to higher values of the applied external magnetic fieldH _a. The results are discussed in terms of the theoretical calculations given byWegener. The data can be fitted using a maximum internal fieldH _max=(598±10) kOe and two atomic spin correlation times τ_c=2,4 · 10^?9 sec andτ′ _c=2,1 · 10^?9 sec.τ _c andτ′ _c are independent ofH _a and the temperatureT. It is assumed in the analysis that the distribution w(H) of the internal fields can be described by a continuous function of the Boltzmann factor type with two parameters. These two parameters are determined by the normalization and the macroscopic magnetization.     

Theory and experiment: Anion binding property of novel phenanthroline or aromatic bridged compounds

A series of artificial compounds, phenanthroline or aromatic bridged indoline derivatives, have been designed and synthesized. The interaction of these compounds with biologically important anions fluoride (F^?), acetate (AcO^?), dihydrogen phosphate (H₂PO₄^?), chloride (Cl^?), bromide (Br^?) and iodide (I^?) was determined by UV–vis, fluorescene titration and theoretical experiments. Results indicate that compound 1 (Di((1″,2″-dihydro-indol-3″-one-2″-hydrazone-1′-hydrazyl)-2′-methylene)-1,3-did-ehydebenzo) and 2 (Di((1″,2″-dihydro-indol-3″-one-2″-hydrazone-1′-hydrazyl)-2′-methylene)-1,3-didehyde-5-nitrobenzo) containing aromatic bridge do not show binding ability for various anions, and that compound 3 (Di((1″,2″-dihydro-indol-3″-one-2″-hydrazone-1′-hydrazyl)-2′-methylene)-2,9-dial-dehyde-1,10-phenanthroline) containing phenanthroline bridge shows the strongest binding ability for F^? among various anions, the moderate binding ability for AcO^? and H₂PO₄^?, and almost no binding ability for Cl^?, Br^?, I^?. The different binding ability of aromatic and phenanthroline bridged compounds may be related to the conjugative effect. What's more, the binding ability of compound 3 with F^? is not interfered by the existence of other anions. Hence, theoretical investigations explore the reasons of different binding ability between compound 3 and anions.     

Structural chemistry and zeolitic properties of mixed oxalates with two open-framework types based on eight coordinate metals

Two families of open-framework materials have been obtained from the assembly of MO₈ polyhedra and oxalate groups as building blocks. The compounds can be formulated as [MM′(C₂O₄)₄]²⁻(M″_y)²⁺ · (4 + x)H₂O (y is 2 for monovalent M″ metals and 1 for divalent M″ metals), in which the sum of the valences of the two metals M and M′ involved in the anionic framework is six. The water molecules and counter cations, located in the voids of the structure, lead to zeolitic or cation dynamic properties.     

Photoionization and photoelectron angular distribution for H2

Photoionization of H₂(¹Σ_g⁺) in a vibrational υ″ and rotational N″ state into H₂⁺(²Σ_g⁺) in a vibrational υ′ and rotational N′ state is studied theoretically. The differential cross section, after summing over the final states, is expressed in the well-known simple form of $\text{(}\text{σ}{}_{\mathrm{T}}\text{4π}\text{)[1 + βP}{}_2\text{(}\text{cos}\text{θ)]}$. Parallel expressions are obtained for H₂⁺ in a specific υ′ state (in terms of σ(υ′) and β(υ′)) and for H₂⁺ in a rotational fine level υ′N′ (in terms of σ(υ′N′) and β(υ′N′)). Asymmetry parameters β, β(υ′) and β υ′N′), which are expressed in terms of Racah and Clebsch-Gordan coefficients and electronic transition moments, can be reduced approximately to 2 lineary polarized light and to -1 for unpolarized light. Using single-center electronic wave functions and including partial eaves l = 1, 3, and 5, σ(υ′) and β(υ′) are computed as a function of υ′ at 584 Å. The computed σ(υ′) divided by the Frank-Condon overlap, in agreement with experimental results, increases monotonically with υ′; σ_T and β are computed in the incident photon energy range of 600–4000 Å and the results compare favorably with previous calculations.     

A theoretical study of hydrogen adsorption on Li, Be, Na, and Mg atoms attached to aromatic hydrocarbons

The binding energy of a hydrogen molecule on metal atoms (Li, Be, Na, and Mg) attached to aromatic hydrocarbon molecules (benzene and anthracene) was calculated using an ab initio molecular orbital method at the MP2(FC)/cc-pVTZ level with basis set superposition error (BSSE) correction. The energy tended to become more negative as the metal atom had a more positive charge and a smaller radius. The energies of Li₂C₆H₆-H₂, Li₂C₁₄H₁₀-H₂, Na₂C₁₄H₁₀-H₂, and MgC₁₄H₁₀-H₂ were −2.7 to −2.2, −4.0 to −3.1, −2.8 to −0.3, and −1.3 kcal/mol, respectively. Most of these energies were more negative than those on the hydrocarbons without metal atoms (ca. −1 kcal/mol). Analyzing the Lennard–Jones type potential with the parameters determined by the MP2 calculations, it was found that these energies mainly consisted of the induction force caused by the positive charge of the metal atom and the dispersion force from the nearest C₆-ring. The energy of BeC₁₄H₁₀-H₂ was more negative (−8.6 kcal/mol) than of the other complexes. The hydrogen molecule in this complex had a comparatively longer H–H distance and a more positive H₂ charge than the others. These data suggest that the hydrogen adsorption on this complex involves a charge transfer process in addition to physisorption interactions. The hydrogen binding energies in some Li₂C₁₄H₁₀-H₂ systems (∼−4.0 kcal/mol) and BeC₁₄H₁₀-H₂ are promising to operate hydrogen storage/release at ambient temperature with moderate pressure.     

Theory of the Relaxation spectra of polymer networks with included hard rodlike particles manifested in NMR

A theory of nuclear magnetic resonance relaxation of¹³C nuclei and nuclear Overhauser effect (NOE) of polymer networks with included rodlike particles is developed for the case when the length of each rod is comparable or greater than the average distance between neighboring crosslinks. The long-scale dynamics of the network is described by means of a regular cubic “coarse-grained” model. The effects of entanglements of long rods in the network are described by a quasi-elastic potential acting between rods and network fragments. The frequency dependences of 1/T _1C and NOE are calculated for the case when the internuclear vector is directed along each rodlike particle. The frequency dependences of 1/T _1C and NOE for rods included into a polymer network are shifted to high frequencies as compared with these dependences for free rods due to quasi-elastic interactions between rods and network fragments. At strongly different viscoelastic parameters of rods and network fragments, the frequency dependences of 1/T_1C and NOE may have two maxima. The high-frequency maximum corresponds to localized motions of rods at immobile network domains. The low-frequency maximum is caused by involving rods in long-scale network motions. The intensity of the low-frequency maximum increases when the degree of interactions between rods and the network increases.     

Dependence of the H2-H2 Interaction on the Monomer Bond Lengths: Steps Toward an Accurate ab initio Estimate

We compute the vibrational coupling between two H₂ molecules from ab initio quantum chemical calculations of the H₂-H₂ potential carried out at the full configuration interaction level of theory using the atom-centered aug-cc-pVTZ basis set for hydrogen. We compare the full configuration interaction results with those obtained using two variants of coupled cluster theory and find that a fully iterative treatment of connected triples may be required to estimate the H₂-H₂ vibrational coupling accurately using coupled cluster theory.     

Vibrationally inelastic scattering of H∼ ions from H2, N2, O2 and CO2

State-resolved measurements are presented for vibrational excitation of H₂, N₂, O₂ and CO₂ by H^? impact in the collision energy rangeE _cm=20–180 eV and for scattering in the forward direction (0±0.5°). The data obtained from the measurements are the relative intensities and differential cross sections for vibrational excitation up toν′=4, the transition probabilitiesP _0→ν′ and the vibrational energy transferΔE _vib. For the systems H^?-H₂, N₂, O₂ the vibrational inelasticity increases in the order H₂-N₂-O₂. The mechanism for vibrational excitation in these systems is due to transient charge transfer from the H^? ion into antibonding orbitals of the target molecule which provides a bond stretching force during the collision. For H₂ and N₂, the results are compared with corresponding measurements for H⁺ scattering where the interaction mechanism is quite different. In the case of CO₂, vibrational excitation in forward scattering is caused primarily by the long-range dipole interaction. The spectra are very similar for H^?-CO₂ and H⁺-CO₂. Finer details are attributed to the influence of transient charge transfer and valence interactions.     

Nuclear spin–lattice relaxation and complex motion of macromolecules in solution

The NMR spectral densities of a complex motion consisting of a combination of anisotropic overall motion and internal motion have been derived. Two approximations of the equations derived for the cases of slow, J_slow (ω), and fast, J_fast (ω), internal motions are presented. These equations imply that reduction in spectral density of overall motion can be observed if the maxima of internal and overall motions spectral densities versus temperature are well separated, as for fast internal motion. Slow intramolecular motion influences the values of spectral densities of the overall motion if one of the two spins performs a motion, for example a proton in double minimum of the ¹⁵N-H?···?N hydrogen bond. The analysis presented reveals small differences between the temperature dependencies of spectral densities of the isotropic and anisotropic overall motions. The theory is illustrated by the ¹³C protonated carbon spin-lattice relaxation of α-cyclodextrin macromolecule, using the expected motional parameters: D _∥/D _⊥?≈?5 at room temperature and for a fast or slow internal motion.     

Internal dynamics of (H2O)2 and (D2O)2 dimers: II. Effective operators of physical quantities with account of inversion and exchange motions

Using the symmetry group chain methods, a model of the internal dynamics of (H₂O)₂ and (D₂O)₂ dimers that takes into account their real geometries and two nonrigid motions with the lowest energy barriers is constructed. The motions are the inversion motion (or the acceptor switching) and the exchange motion of the acceptor and donor via an intermediate trans configuration. The model rigorously describes the interactions of various motions and leads to a simple algebraic scheme of calculation of both the positions of the levels in the energy spectrum and the intensities of transitions between them. It is important that the correctness of the model is limited only by the trueness of the choice of the symmetry of the internal dynamics.     

Effect of Ti4+ ions on the magnetic and dielectric properties of Mg-ferrite

X-ray diffraction, the real part (ε′), the imaginary part (ε″) of dielectric constant, and the molar magnetic susceptibility (χ_M) for Mg_1+xTi_xFe_2−2xO₄ ferrite (0.1⩽x⩽0.9) were studied. The date of X-ray diffraction showed that the unit cell parameter increases with Ti concentration and ascribed to the predicted variation of the cation distribution, while Mg²⁺ ions are highly diffusible and very sensitive to heat. The effect of dilution by Ti ions is discussed in terms of increasing superparamagnetic and single domain (SP/SD) grains. The measurements of ε′ were performed at different temperatures as a function of frequency, while the magnetic susceptibility was studied at different magnetic field intensities. The variation of the dielectric properties depends mainly on the valence exchange between the different metal ions in the same site or in different sites. All parameters such as ε′, ε″, χ_M showed a decrease in value with increasing Ti and Mg concentration. The dispersion in ε′ with frequency disappeared gradually with increasing Ti concentration.     

Theoretical considerations regarding the defect structure of M1−xO cubic oxides for small departures from stoichiometry

This study examines the discrepancy between two models of defect structure proposed for M_1?xO cubic oxides with small departures from stoichiometry. One, involving vacancy aggregates such as 4:1 or 6:2 clusters is deduced by Callow et al. from the calculated defect formation energies. The other, involving free unassociated vacancies V″_M and V′_M is used by many authors to interpret their experimental results.In the particular case of M_1?xO, for which accurate thermodynamic data are available for 1273 K< T < 1423 K, it is shown that, between these two models, only the latter is consistent with the experimental ΔG(O₂) values and that the concentrations of clusters are negligible over the whole homogeneity range. Furthermore, the unassociated defect formation energies calculated by Catlow et al. [27] do not satisfactorily account for the experimental values of ΔH(O₂).     

Nonlinear dynamics of domain walls with a vortex internal structure in magnetouniaxial films with planar anisotropy

The nonlinear and generally unsteady dynamics of domain walls with a vortex internal structure in a constant magnetic field H is investigated on the basis of the numerical solution of the Landau-Lifshitz equation for a 2D distribution of magnetization M in magnetic films with planar anisotropy taking into account exactly the main interaction, including the dipole-dipole interaction. It is shown that in addition to field H _c (bifurcation field) above which the motion of a wall becomes unsteady and its internal structure experiences global dynamic changes, there exists a field H₀ separating two steady motions of the wall with different structures. The data clarifying the physical origin of the nonlinear dynamic rearrangement of the wall structure are presented. New rearrangement mechanisms associated with the generation and attenuation of vortices as well as their tunneling through the central surface of the wall are established. The existence of subperiod oscillations of the wall velocity in a static field in addition to the oscillations associated with the precession of M around the easy magnetization axis is predicted. The period T of dynamic variations of the wall structure is studied, and an empirical formula is proposed for describing the singular behavior of the T(H) dependence near H=H _Hc with the critical index depending on the film parameters. The bifurcation process is studied, and a nonlinear dependence of the critical field H _c on the film thickness and the saturation magnetization is established. The possibility of direct experimental investigation of the dynamic rearrangement of the internal structure of the wall is indicated.     

Low-temperature plasticity and lattice dynamics of solid parahydrogen with an isotopic impurity

The low-temperature plasticity of solid polycrystalline parahydrogen doped with an isotopic impurity (deuterium) is studied. The dependences of the rate of steady-state creep in p-H₂ on the impurity concentration and stress are obtained. The deformation of p-H₂ is described with inclusion of the zero-point mean-square displacements 〈x²〉 of particles making up a crystal. The calculated and experimental values of 〈x²〉 are compared for two possible isotope molecules (HD and D₂) at three stress levels. A correlation between the 〈x²〉 values and an increase in the force constants of a p-H₂ crystal doped with the isotopic impurity is established. An increase in the mean-square displacements of p-H₂ with the tensile load is discussed. Deformation-induced purification of a p-H₂ crystal from the isotopic impurity is suggested to occur.     

Microwave spectrum of the heterodimers: CH3OH-CO2 and CH3OH-H2CO

Molecular complexes, dimers and heterodimers often show interesting structures, large amplitude internal motions and orientations for reaction coordinates. These properties were the motivations for the current study of the rotational spectra of the heterodimers, CH₃OH-CO₂ and CH₃OH-H₂CO, in a pulsed nozzle Fourier-transform microwave (FTMW) spectrometer. In addition to studying the normal isotopic forms, several isotopologues containing ¹³C or deuterium substituted atoms of each heterodimer were analyzed in order to obtain structural data of the complexes. All species showed splittings from internal rotation of the methyl group and splittings on the b-type transitions of the CH₃OH-H₂CO species suggesting rotation of the H₂CO group between equivalent structural forms. Stark effect measurements on each of the parent species provided dipole moment components. Theoretical ab initio results are compared to the experimentally determined molecular parameters.     

Assignments of Nonexchangeable Proton Resonances and the Solution Structures of d–TGGGT

In this paper, we report the studies of the solution structures of synthetic pentadeoxyribonucleotide d-TGGGT(NH₄ ⁺ salt) using 2D–NMR. The 1H–NMR experiments with different temperatures and concentrations reveal an equilibrium between single strand and aggregation. In the experimental condition(22°C, 13mmol/ L), the cross peaks in the COSY spectrum are mainly from single strand, and the spin systems of sugar resonances of this component can be assigned. In contrast, the cross peaks in the NOESY spectrum mainly come from aggregation and the sequential assignments of bases, sugar 1′, 2′ and 2″ protons can be carried out. From NOE connectivities, it is obvious that the aggregation adopts a right–handed helix conformation. It is suggested that the aggregation in our experiment corresponds to the tetramolecular complex.     

A perturbation theory study of H2 on LiF(0 0 1)

In response to recent helium atom scattering (HAS) results, Monte Carlo (MC) simulations and perturbation theory have been performed for H₂ on LiF(0 0 1). MC simulations predict that H₂ molecules form a series of structures, p(2 × 2), p(8 × 2), p(4 × 2) with coverages Θ = 0.5, 0.625 and 0.75, respectively, that are stable up to 8 K. This is in partial agreement with the HAS results that report c(2 × 2) and c(8 × 2) structures; they agree in terms of coverage and stability, but disagree in terms of symmetry. To reconcile the results of the simulations and experiments, the orientation of the adsorbed H₂ molecules was studied using perturbation theory. These calculations show that the adsorbed H₂ molecules are azimuthally delocalized and that the structures are c-type rather then p-type. The calculations also indicate that p-H₂ and helicoptering o-H₂ prefer cationic sites, while cartwheeling o-H₂ prefers anionic sites.