Equation of state of CaMnO3: a combined experimental and computational study

Elastic properties of CaMnO₃ are of primary importance in the science and technology of CaMnO₃-based perovskites. From X-ray diffraction experiments performed at pressures up to 100 kbar using a diamond-anvil cell to hydrostatically compress our sample, a bulk modulus, K ₀, of 1734(96) kbar was obtained after fitting parameters to the third-order Birch–Murnaghan equation of state. Mean field, semiclassical simulations predict, for the first time, the third-order equation-of-state parameters and show how the bulk modulus increases with pressure (the zero pressure value being 2062.1 kbar) and decreases with the extent of nonstoichiometry caused by the formation of oxygen vacancies. These trends are amplified for the shear modulus. A more accurate model that allows for the explicit reduction of Mn ions, or localization of excess electrons, yields qualitatively similar results. The experimental and calculated axial ratios show the same trends in their variation with rising pressure.     

Two clarifications on the likelihood surface in functional models

The paper consists of two parts. In the first part a previous result by Solari [(1969) J. Roy. Statist. Soc. Ser. B31] for a simplified two-variable model is generalized to the multivariate case. In the second part the behaviour of the likelihood surface is clarified when we have replications of observations.     

Self-consistent field theory of dilated atomic hamiltonians: Some remarks

The bi-variational SCF scheme for dilated closed shell atomic hamiltonians is studied and discussed. Applications to the Be atom are presented.     

The Ackermann function. a theoretical,computational, and formula manipulative study

Ackermann's function is of highly recursive nature and of two arguments. It is here treated as a class of functions of one argument, where the other argument defines the member of the class. The first members are expressed with elementary functions, the higher members with a hierarchy of primitive recursive functions. The number of calls of the function needed in a straightforward recursive computation is given for the first members. The maximum depth in the recursion during the evaluation is investigated.Results from tests with the Ackermann function of recursive procedure implementations in ALGOL-60, ALGOL W, PL/I and SIMULA-67 on IBM 360/75 and CD 6600 are given.A SYMBAL formula manipulating program, that automatically solves recurrence relations for the first members of the function class and for the number of calls needed in their straightforward computation, is given.The Ackermann rating of programming languages is discussed.     

Calculation of some magnetic and electric fields with cylindrical symmetry

Summary It is assumed that the magnetic and electric fields have cylindrical symmetry and at the same time mirror symmetry with respect to a median plane. The field strength in the median plane is given. The problem is to calculate the field at an arbitrary point in space, the equipotential surfaces, and the form of the polepieces of magnets. Solutions are given in the form of power expansions. Analytical solutions are given when the field strength in the median plane as a function of the radius is a polynomial.     

Vibrational motion in isotopomers of the HeH+ molecular ion: An application of the electron nuclear dynamics method

The importance of isotopic substitution as a tool for elucidation of chemical reaction events originates in the fact that the Coulombic Hamiltonian is isotopically invariant except for the nuclear kinetic energy term. Thus, in theories of isotope effects based on the Born-Oppenheimer scheme, the basic presumption is the invariance of the potential energy surface (PES). We use, however, a fully dynamic approach, called Electron Nuclear Dynamics (END), which does not require a preconstructed PES. Since the END formalism is rather different from commonly used procedures, we study the anharmonic nuclear vibration in isotopic species of the HeH⁺ molecular ion as a model problem. A single time-dependent complex parametrized determinantal wave function is used for the electrons and the nuclei are treated classically. The time evolution of the nuclear and electronic dynamical variables obtained by integration of equations of motion are reported as bond length, nuclear kinetic energy, and Mulliken populations. The molecule vibrates as a classical object. The product of the reduced mass and the square of the vibrational frequency is isotopomer invariant for any common total energy. The difference between the total energy and the nuclear kinetic energy as a function of the internuclear distance is interpreted as the average dynamic potential. © 1997 John Wiley & Sons, Inc.     

Atmospheric chemistry of C3-C6 cycloalkanecarbaldehydes

The rate coefficients for the gas phase reaction of NO3 and OH radicals with a series of cycloalkanecarbaldehydes have been measured in purified air at 298 +/- 2 K and 760 +/- 10 Torr by the relative rate method using a static reactor equipped with long-path Fourier transform infrared (FT-IR) detection. The values obtained for the OH radical reactions (in units of 10(-11) cm3 molecule(-1) s(-1)) were the following: cyclopropanecarbaldehyde, 2.13 +/- 0.05; cyclobutanecarbaldehyde, 2.66 +/- 0.06; cyclopentanecarbaldehyde, 3.27 +/- 0.07; cyclohexanecarbaldehyde, 3.75 +/- 0.05. The values obtained for the NO3 radical reactions (in units of 10(-14) cm3 molecule(-1) s(-1)) were the following: cyclopropanecarbaldehyde, 0.61 +/- 0.04; cyclobutanecarbaldehyde, 1.99 +/- 0.06; cyclopentanecarbaldehyde, 2.55 +/- 0.10; cyclohexanecarbaldehyde, 3.19 +/- 0.12. Furthermore, the reaction products with OH radicals have been investigated using long-path FT-IR spectroscopy and proton-transfer-reaction mass spectrometry (PTR-MS). The measured carbon balances were in the range 89-97%, and the identified products cover a wide spectrum of compounds including nitroperoxycarbonyl cycloalkanes, cycloketones, cycloalkyl nitrates, multifunctional compounds containing carbonyl, hydroxy, and nitrooxy functional groups, HCOOH, HCHO, CO, and CO2.     

Triplet—triplet absorption spectra of alternant hydrocarbons within the grand canonical time-dependent hartree—fock approximation

Triplet—triplet excitation energies and transition moments have been calculated for some alternant hydrocarbons by the grand canonical time-dependent Hartree—Fock approximation within the Pariser—Parr—Pople model. The main features of the experimental spectra are found to be reproduced more consistently in this scheme than in previously applied models.