Theoretical predictions of the spectroscopic parameters in noble-gas molecules: HXeOH and its complex with water

We employ state-of-the-art methods and basis sets to study the effect of inserting the Xe atom into the water molecule and the water dimer on their NMR parameters. Our aim is to obtain predictions for the future experimental investigation of novel xenon complexes by NMR spectroscopy. Properties such as molecular structure and energetics have been studied by supermolecular approaches using HF, MP2, CCSD, CCSD(T) and MP4 methods. The bonding in HXeOH···H(2)O complexes has been analyzed by Symmetry-Adapted Perturbation Theory to provide the intricate insight into the nature of the interaction. We focus on vibrational spectra, NMR shielding and spin-spin coupling constants-experimental signals that reflect the electronic structures of the compounds. The parameters have been calculated at electron-correlated and Dirac-Hartree-Fock relativistic levels. This study has elucidated that the insertion of the Xe atom greatly modifies the NMR properties, including both the electron correlation and relativistic effects, the (129)Xe shielding constants decrease in HXeOH and HXeOH···H(2)O in comparison to Xe atom; the (17)O, as a neighbour of Xe, is deshielded too. The HXeOH···H(2)O complex in its most stable form is stabilized mainly by induction and dispersion energies.     

Dynamics of fibers in a wide microchannel

Dynamics of single flexible non-Brownian fibers, tumbling in a Poiseuille flow between two parallel solid plane walls, is studied with the use of the HYDROMULTIPOLE numerical code, based on the multipole expansion of the Stokes equations, corrected for lubrication. Fibers, which are closer to a wall, more flexible (less stiff) or longer, deform more significantly and, for a wide range of the system parameters, they faster migrate towards the middle plane of the channel. For the considered systems, fiber velocity along the flow is only slightly smaller than (and can be well approximated by) the Poseuille flow velocity at the same position. In this way, the history of a fiber migration across the channel is sufficient to determine with a high accuracy its displacement along the flow.     

Approximate variation-perturbation calculations of second-order molecular properties

The variation-perturbation method is applied to the calculation of the magnetic susceptibility of diatomic molecules within the basis of the CNDO/2 SCF wave functions. All the many-centre integrals which appear in the treatment were simplified according to the ZDO approximation.

The calculated diamagnetic contribution is in good agreement with non-empirical results. It agrees also with available experimental data. Although the paramagnetic part of the susceptibility tensor was calculated with a simple two-term form of the variational correction, the results are comparable to those obtained in more advanced ab initio treatments. Also the computed total magnetic susceptibility of various diatomic molecules is in substantial agreement with non-empirical results. A comparison is made with the results of other semi-empirical calculations based on the CNDO/2 SCF wave functions. It follows that the results of the present method are remarkably better.     

Ammonia dimer, linear or cyclic?

Ab initio calculations have been carried out for ammonia dimers with 4-31G and 6-31G* basis sets. The results are corrected for basis-set superposition error. For the ammonia dimer, the stability of the linear form is comparable to that of the cyclic form. The localized orbitals for both dimers are discussed.     

Determination of loads applied perpendicularly to the outer boundary of a ring using coefficients of influence

A procedure is explained to determined the amount of several pairs of diametrical loads applied to the outside boundary of a ring when stresses at selected points of the inside or outside boundaries are known. Coefficients of influence are used, following an approach similar to the one presented in a previous paper. Examples of application are given and the possible increase in precision is shown when the number of points of measurements is larger than the number of loads to be determined.     

Thermodynamics and kinetics of intramolecular proton transfer in Guanine. Post Hartree-Fock study

The most stable tautomers and rotamers of guanine are characterized by post Hartree-Fock ab initio calculations at the MP2 and CCSD(T) levels employing extended basis sets. Four of the lowest-energy structures (7H-oxo-amino- < 9H-oxo-amino- < 9H-syn-hydroxo-amino- < 9H-anti-hydroxo-amino-guanine) are found to lie within ca. 1 kcal/mol. The next form of guanine is established to lie more than 3 kcal/mol higher than the global minimum tautomer. The transition states of the following reversible reactions: 9H-oxo-amino-guanine right harpoon over left harpoon 9H-syn-hydroxo-amino-guanine right harpoon over left harpoon 9H-anti-hydroxo-amino-guanine have been studied. The calculated energy data were used to obtain thermodynamic parameters and to estimate the composition of the equilibrium mixture of conformers at 0 K and room temperature. The rate constants for the tautomerization of 9H-oxo-amino-guanine were determined by using the instanton approach. Their predicted values characterize an extremely slow chemical process, which is expected to reach the equilibrium in ca. 2500 h. Despite being so slow, we have shown that such a rate of the tautomerization describes a process that is much faster than the one characterized by the observed frequency of spontaneous point mutations. Therefore, additional stabilization factors, e.g., hydrations and interactions with enzymes are necessary to secure the known fidelity of DNA synthesis.     

Electric properties of the chloride ion

The dipole (), quadrupole (C), and dipole-quadrupole (B) polarizabilities and the dipole hyperpolarizability () of the chloride ion have been calculated by using the many-body perturbation theory approach and a series of large polarized GTO/CGTO basis sets. The complete fourth-order treatment of the electron correlation effects with a basis set comprising the s, p, d, f, and g functions gives: =38.01 a.u., C=211.5 a.u., B=–5.14×10³ a.u., and =128. 5×10³ a.u. as compared to the corresponding SCF values (=31.49 a.u., C=158.9 a.u., B=–2.92×10³ a.u., =57.7×10³ a.u.). The quenching of polarizabilities of the Cl^– ion in solutions and ionic crystals is discussed.     

Solvation states of HCl in mixed ether:acid crystals: a computational study

Acid solvation states are investigated in the recently discovered mixed ether:acid crystalline solids. The solids are simulated using on-the-fly molecular dynamics as implemented in the density functional code QUICKSTEP employing Gaussian basis sets. The solids are shown to display a remarkably broad range of acid solvation states, depending on the ether:acid ratio, including proton sharing in the 1:1 case, proton transfer to the ether in 1:2, and perturbed molecular acid in 1:6. The observed variation of the infrared spectra with the composition is accounted for qualitatively with the help of the calculations.