Magnetic resonance tensors in Uracil: Calculation of 13C, 15N, 17O NMR chemical shifts, 17O and 14N electric field gradients and measurement of 13C and 15N chemical shifts

The experimental ¹³C NMR chemical shift components of uracil in the solid state are reported for the first time (to our knowledge), as well as newer data for the ¹⁵N nuclei. These experimental values are supported by extensive calculated data of the ¹³C, ¹⁵N and ¹⁷O chemical shielding and ¹⁷O and ¹⁴N electric field gradient (EFG) tensors. In the crystal, uracil forms a number of strong and weak hydrogen bonds, and the effect of these on the ¹³C and ¹⁵N chemical shift tensors is studied. This powerful combination of the structural methods and theoretical calculations gives a very detailed view of the strong and weak hydrogen bond formation by this molecule. Good calculated results for the optimized cluster in most cases (except for the EFG values of the ¹⁴N3 and ¹⁷O4 nuclei) certify the accuracy of our optimized coordinates for the hydrogen nuclei. Our reported RMSD values for the calculated chemical shielding and EFG tensors are smaller than those reported previously. In the optimized cluster the 6-311+G** basis set is the optimal one in the chemical shielding and EFG calculations, except for the EFG calculations of the oxygen nuclei, in which the 6-31+G** basis set is the optimal one. The optimal method for the chemical shielding and EFG calculations of the oxygen and nitrogen nuclei is the PW91PW91 method, while for the chemical shielding calculations of the ¹³C nuclei the B3LYP method gives the best results.     

Broadband radiation transport in an optically dense gas in the presence of an RF field

The variational Monte Carlo method is applied to investigate the ground state and some excited states of the lithium atom and its ions up to Z = 10 in the presence of an external magnetic field regime with γ = 0–100 arb. units. The effect of increasing field strength on the ground state energy is studied and precise values for the crossover field strengths were obtained. Our calculations are based on using accurate forms of trial wave functions, which were put forward in calculating energies in the absence of magnetic field. Furthermore, the value of Y at which ground-state energy of the lithium atom approaches to zero was calculated. The obtained results are in good agreement with the most recent values and also with the exact values.     

超强磁场对中子星外壳层核素56Fe,56Co,56Ni,56Mn和56Cr电子俘获过程中微子能量损失的影响

研究了超强磁场对中子星外壳层核素⁵⁶Fe,⁵⁶Co,⁵⁶Ni,⁵⁶Mn和⁵⁶Cr电子俘获过程中微子能量损失的影响.结果表明,就大部分中子星表面的磁场B<10¹³G,超强磁场对中微子能量损失率的影响很小.对于一些磁场范围为10¹³—10¹⁵G的超磁星,超强磁场可使中微子能量损失率大大降低,甚至超过5个数量级.     

Thermodynamic functions of a nonrelativistic degenerate neutron gas in a magnetic field

The Fermi energy, partial concentrations of polarized neutrons, pressure, and volume energy density of a degenerate nonrelativistic neutron gas in a magnetic field are calculated using numerical methods taking into account the anomalous magnetic moment of a neutron. The results of calculations are a generalization of relations underlying the Oppenheimer-Volkov model of a neutron star to the case of an applied magnetic field. An ultrastrong (up to 10¹⁷ G) magnetic field changes the pressure and internal energy of the star and affects it static configuration and evolution. It is shown that a degenerate neutron gas in ultrastrong and weak magnetic fields is paramagnetic; the corresponding values of magnetic susceptibility differ by a factor on the order of unity. The possibility of experimentally verifying the results from analysis of pulsar-emitted radiation is discussed.     

Ro-vibrational states of triplet H3 (aΣu): The lowest 19 bands

We have performed extensive calculations of the ro-vibrational states of triplet H₃⁺, using the method of hyperspherical harmonics and our recently reported double many-body expansion potential energy surface. The rotational term values of the lowest 19 states are presented here for a total angular momentum of J?10.     

TDPAD measurements of magnetic hyperfine field for <Superscript>132</Superscript>Ba in ferromagnetic Ni

The magnetic hyperfine field of Ba in ferromagnetic Ni has been measured by time differential perturbed angular distribution technique using the 13 ns 10⁺ isomeric state in ¹³²Ba as probe which was populated in the reaction ¹²C(¹²⁴Sn, 4n) ¹³²Ba at beam energy of 60 MeV. The hyperfine field extracted from the observed Larmor precession frequency comes out to be ?84(5) kG. Our experimental results show good agreement with theoretical calculations performed within local density approximation of the density functional theory. The hyperfine field data presented here would be useful towards accurate determination of g-factor in other high spin states in Ba isotopes.     

High-order perturbation theory for the hydrogen atom in a magnetic field

The states of a hydrogen atom with principal quantum numbers n⩽3 in a constant uniform magnetic field ℋ are studied. Coefficients in the expansion of the energy of these states in powers of ℋ² up to the 75th order are obtained. Series for the energies of the states and the wave functions are summed to values of ℋ on the order of the atomic magnetic field. A generalization of the moment method upon which these calculations are based can be used in other cases in which a hydrogen atom is perturbed by a potential with a polynomial dependence on the coordinates. Zh. éksp. Teor. Fiz. 113, 550–562 (February 1998)     

Variational Calculation of Energies of Highly Excited Rovibrational States of CO2

Accurate variational calculations of energies of highly excited rovibrational states of ¹²C¹⁶O₂ using a Lanczos recursion are presented. In a first step, we use experimental rovibrational transition frequencies to determine by a least-square fitting procedure a potential energy surface for the CO₂ molecule. This potential energy surface is expressed as a multidimensional power series expansion in the normal coordinates. It is then used to determine all the rovibrational energies for symmetry e levels up to a rotational number J=200, a vibrational energy of 13 000 cm⁻¹, and a vibrational angular momentum l=13.     

Two-loop self-energy correction in a strong Coulomb nuclear field

The two-loop self-energy correction to the ground-state energy levels of hydrogen-like ions with nuclear charges Z≥10 is calculated without the Zα expansion, where α is the fine-structure constant. The data obtained are compared with the results of analytical calculations within the Zα expansion; significant disagreement with the analytical results of order α²(Zα)⁶ has been found. Extrapolation is used to obtain the most accurate value for the two-loop self-energy correction for the 1s state in hydrogen.     

Twenty-parameter eigenfunctions and energy values of the 23 S States of He and He-like Ions

Twenty-parameter calculations of the energies and wave functions of the first excited states 2³ S of He, Li⁺, Be⁺⁺, B⁺⁺⁺, O⁶⁺, Ne⁸⁺, Mg¹⁰⁺, have been carried out using Hylleraas' method. The energy values have been corrected for mass polarization. The coefficients of the best wave functions are listed. Similar calculations for the 2³ S state of the H^? ion yield an energy value which cannot be distinguished from the energy of a free H atom. For He and Li⁺, in addition, forty-parameter calculations have been carried out. The results compare well with the recent calculations of Pekeris using a somewhat different method. Even after the inclusion of the relativistic correction, the theoretical energy values deviate slightly from the observed. The differences, ?0·10±0·05 cm^?1 for He and ?1·07±0·10 cm^?1 for Li⁺, represent observed values of the Lamb shifts in the 2³ S states. These values agree within their uncertainties with the values predicted from quantum electrodynamics.     

Band gap and mass renormalisation in GaInP/AlGaInP quantum wells

We report magneto-luminescence studies of dense electron–hole plasmas in compressively strained GaInP/AlGaInP quantum wells. At carrier densities of order 10¹³ cm⁻² many-body effects are investigated. The band gap is reduced by up to 36 meV, much less than expected from conventional random phase approximation calculations. However, much better agreement is obtained on comparison with recent density functional calculations which include the Hartree energy. The reduced mass is found to increase by up to 40% over values from low-excitation measurements. Comparison with other work suggests that the mass renormalisation is substantial in materials with wide band gaps.     

Measurements and calculations of self-broadening coefficients of lines belonging to the v2 band of H216O

The self-broadening coefficients of 150 lines belonging to the v₂ band of H₂¹⁶O between 1770 and 2250 cm^-1 have been measured using Fourier transform spectra (resolution ≈ 0.005 cm^-1). The four different methods which have been used to deduce the self-broadening coefficients from experiment are described in detail. The estimated average uncertainty is about 15% and varies from 7 to 30%, depending on the method used and on the line involved. Two theoretical calculations, one based on the Anderson-Tsao-Curnutte method and the other on the recent method proposed by Davies, have been performed, retaining only the dipole-dipole interaction. For some lines of the v₂ band and for some pure rotation lines, calculations based on other formalisms have also been performed. For all of these calculations, we have used accurate spectroscopic data: precise energy levels, realistic wavefunctions, and a complete dipole-moment operator expansion in order to compute the transition probabilities. As compared to the previously calculated values of the pioneering work of Benedict and Kaplan, where the Anderson-Tsao-Curnutte method was used, our calculations show improvements by about 14% in the agreement between measured and calculated self-broadening coefficients.     

Expansion of spark channels in air and possibilities of plasma crowbar in high pulsed current and magnetic field technique

The radial expansion velocities and diameters of spark channels in air are measured by the plasma-metal contact method. An LC discharge circuit with energy up to 50 kJ and with current frequencies ranging from ∼10² to ∼10⁴ Hz served as the source of the channels. It is concluded on the basis of the results obtained that the previously proposed automatic plasma crowbar based on the expansion of spark channels in gases is a universal switch for an inductive load in LC discharge circuits that could find very wide applications in high pulsed current and magnetic field technology. Zh. Tekh. Fiz. 68, 133–136 (February 1998)     

On the evaluation of high-order interaction energies using pseudo state methods

General expressions for the coefficients of the R ^-1 multipole expansion of the third and fourth-order interaction energies are derived in (pseudo) spectral form for the interaction of two S-state atoms. Explicit accurate results, for the H(ls)-H(ls) interaction, are obtained for the lead O(R ^-11) third-order energy and the lead O(R ^-12) fourth-order energy by using one centre pseudo state methods. These calculations, together with the appropriate second-order results, furnish an accurate expression for the total long-range interaction energy through O(R ^-12) and illustrate the applicability of the pseudo state approach for the evaluation of high-order interaction energies.     

The Hyperfine Structure of the Ground State in the Muonic Helium Atoms

Non-relativistic ionization energies ³He²⁺μ^?e^? and ⁴He²⁺μ^?e^? of helium-muonic atoms are calculated for ground states. The calculations are based on the variational method of the exponential expansion. Convergence of the variational energies is studied by an increasing of a number of the basis functions N. This allows to claim that the obtained energy values have 26 significant digits for ground states. With the obtained results we calculate hyperfine splitting of the muonic helium atoms.     

Mechanistic and kinetics study of the gas phase reactions of methyltrifluoroacetate with OH radical and Cl atom

Theoretical investigations are carried out on the title reactions by means of ab initio and DFT methods. The optimized geometries, frequencies and minimum energy path are obtained at MPWB1K/6-31+G(d,p) level. Single point energy calculations are performed at MP2 and QCISD(T) levels of theory. Energetics were further refined by calculating the energy of the species with a high level G2(MP2) method. The rate constant of the two reactions are calculated at 298?K and 1?atm using Canonical Transition State Theory (CTST) utilizing the ab initio data obtained during the present study. The rate constant values are found to be 5.5?×?10^?14 and 5.9?×?10^?14?cm³ molecule^?1 s^?1, respectively which are in good agreement with the experimental data.     

Comparison of Triton Bound-State Properties Using Different Separable Representations of Realistic Nucleon-Nucleon Potentials

 The quality of two different separable expansion methods (W-matrix and Ernst-Shakin-Thaler) is investigated. We compare the triton binding energies and components of the triton wave functions obtained in this way with the results of a direct two-dimensional treatment. The Paris, Bonn A and Bonn B potentials are employed as underlying two-body interactions, their total angular momenta being incorporated up to . It is found that the most accurate results based on the Ernst-Shakin-Thaler method agree within 1.5% or better with the two-dimensional calculations, whereas the results for the W-matrix representation are less accurate. Received February 9, 1999; accepted for publication February 13, 1999     

Calculations of Coulomb systems with optimization of nonlinear parameters

Precise variational calculations of the energy and diverse physical characteristics are performed for the ground state of a fully nonadiabatic four-particle system—the positronium molecule e⁺e^?e⁺e^?. The nonlinear exponential parameters of correlated Gaussian basis functions dependent on all interparticle separations are systematically optimized. The dependence of the calculated energy values and the expectation values of interparticle separations (as well as their degrees and Dirac delta functions of interparticle separations) on the basis size N is examined. For N=200, the ground-state energy of the positronium molecule is found to be E=?0.5160028 au. For an extended basis set with N=4700 containing 200 basis functions with the optimized parameters and 4500 additional functions with random values of nonlinear parameters, E=?.5160036 au. At present, this result is the most accurate variational energy value of the positronium molecule, and it demonstrates the high efficiency of optimization of the nonlinear parameters in calculations of atomic-molecular systems. The lifetime of the positronium molecule e⁺e^?e⁺e^? with respect to electron-positron annihilation is calculated to be τ=2.26×10^?10 s.     

Discussion of the He-He interaction energy in the average energy approximation

Using the Unsöld average energy method a double perturbation theory expression for the interaction energy through second order is obtained which includes intra-atomic correction terms arising from the use of trial wavefunctions to represent the non-interacting molecules. These formal expressions are applied to the ground state He-He interaction and results for the interaction energy are obtained that compare favourably with recent semiempirical and ab initio calculations. The Unsöld calculations are used to investigate approximations that have been introduced into the average energy calculation by other workers, and as a model for discussing the relative importance of second-order charge overlap and exchange effects and the convergence of the multipole treatment of the interaction energy for this typical non-bonded interaction. The results illustrate the importance of knowing as many terms as possible in the R ^-1 expansion of the energy. Finally a portion of this work required the recalculation of the He-He repulsive energy obtained by using the Eckart wavefunction to represent the helium atom. The resultant energy is approximately 25 per cent lower than that previously obtained using this wavefunction for most values of R.