The calculation of force constants and normal co-ordinates--VII Normal co-ordinates in the E species of allene

Force constant and normal co-ordinate calculations are reported for the E species vibrations of the allene molecule. Data on the fundamental vibration frequencies of allene-h4, allene-d4 and allene-1.1-d2 and on the five experimentally determined Coriolis zeta constants of C3H4 and C3D4, were used in a force constant refinement procedure. Allowing for product and sum rules this gives 21 independent data which were used to refine to the most general harmonic force field (10 parameters) with one constraint (in the absence of any constraints the refinement was not satisfactory). The results have been used to calculate the complete ζz Coriolis interaction matrix for the allene-1.1-d2 molecule, and hence to calculate the expected rotational structure of the perpendicular bending vibrations of this molecule; the good agreement obtained with the observed spectra is a check on our results.

The F test for comparing two normal variances: correct and incorrect calculation of the two-sided p-value?

This article illustrates that not all statistical software packages are correctly calculating a p-value for the classical F test comparison of two independent Normal variances. This is illustrated with a simple example, and the reasons why are discussed. Eight different software packages are considered.

The determination of molecular properties from MULTIMODE with an application to the calculation of Franck-Condon factors for photoionization of CF3 to CF3+

Extensions to the code MULTIMODE to obtain rovibrational wave functions and properties are described. An application of these new capabilities is made to a calculation of the Franck-Condon factors for photoionization of CF3 to CF3+. These calculations make use of a new, full-dimensional ab initio potential energy surface, which is also described here.

A variational method for the calculation of spin-rovibronic energy levels of any triatomic molecule in an electronic triplet state

The triatomic spin-rovibronic variational code RVIB3 has been extended to include the effect of two uncoupled electrons, for both (3)Sigma(-) and (3)Pi (Renner-Teller) electronic states. The spin-orbital-rotational kinetic energy is included in the usual way, via terms (J+L+S). The phenomenological terms AL.S and lambda 2/3(3S(z)(2)) are introduced to reproduce the 3 spin-orbit and spin-spin splittings, respectively. Calculations are performed to evaluate the spin-rovibronic energy levels of CCO (X) over tilde (3) Sigma(-) and CCO (A) over tilde (3) Pi for which the Born-Oppenheimer potentials are derived from high-accuracy ab initio calculations.

Calculation of converged rovibrational energies and partition function for methane using vibrational-rotational configuration interaction

The rovibration partition function of CH4 was calculated in the temperature range of 100-1000 K using well-converged energy levels that were calculated by vibrational-rotational configuration interaction using the Watson Hamiltonian for total angular momenta J=0-50 and the MULTIMODE computer program. The configuration state functions are products of ground-state occupied and virtual modals obtained using the vibrational self-consistent field method. The Gilbert and Jordan potential energy surface was used for the calculations. The resulting partition function was used to test the harmonic oscillator approximation and the separable-rotation approximation. The harmonic oscillator, rigid-rotator approximation is in error by a factor of 2.3 at 300 K, but we also propose a separable-rotation approximation that is accurate within 2% from 100 to 1000 K. (C) 2004 American Institute of Physics.

Theoretical calculation of absorption intensities of C2H and C2D

The theory of dipole-allowed absorption intensities in triatomic molecules is presented for systems with three close-lying electronic states of doublet multiplicity. Its derivation is within the framework of a recently developed variational method [CARTER, S., HANDY, N. C., PUZZARINI, C., TARRONI, R., and PALMIERI, P., 2000, Molec. Phys., 98,1967]. The method has been applied to the calculation of the infrared absorption spectrum of the C2H radical and its deuterated isotopomer for energies up to 10000 cm(-1) above the ground state, using highly accurate ab initio diabatic potential energy and dipole moment surfaces. The calculated spectra agree very well with those recorded experimentally in a neon matrix [FORNEY, D., JACOX, M. E., and THOMPSON, W. E., 1995, J. molee. Spectrosc., 170, 178] and assignments in the high energy region of the IR spectra are proposed for the first time.

Ligand dynamics in myoglobin: calculation of infrared spectra for photodissociated NO

We present molecular dynamics simulations of the photodissociated state of MbNO performed at 300 K using a fluctuating charge model for the nitric oxide (NO) ligand. After dissociation, NO is observed to remain mainly in the centre of the distal haem pocket, although some movement towards the primary docking site and the xenon-4 pocket can be seen. We calculate the NO infrared spectrum for the photodissociated ligand within the haem pocket and find a narrow peak in the range 1915-1922 cm(-1). The resulting blue shift of 1 to 8 cm(-1) compared to gas-phase NO is much smaller than the red shifts calculated and observed for carbon monoxide (CO) in Mb. A small splitting, due to NO in the xenon-4 pocket, is also observed. At lower temperatures, the spectra and conformational space explored by the ligand remain largely unchanged, but the electrostatic interactions with residue His64 become increasingly significant in determining the details of the ligand orientation within the distal haem pocket. The investigation of the effect of the L29F mutation reveals significant differences between the behaviour of NO and that of CO, and suggests a coupling between the ligand and the protein dynamics due to the different ligand dipole moments.

Efficient on the fly calculation of time correlation functions in computer simulations

Time correlation functions yield profound information about the dynamics of a physical system and hence are frequently calculated in computer simulations. For systems whose dynamics span a wide range of time, currently used methods require significant computer time and memory. In this paper, we discuss the multiple-tau correlator method for the efficient calculation of accurate time correlation functions on the fly during computer simulations. The multiple-tau correlator is efficacious in terms of computational requirements and can be tuned to the desired level of accuracy. Further, we derive estimates for the error arising from the use of the multiple-tau correlator and extend it for use in the calculation of mean-square particle displacements and dynamic structure factors. The method described here, in hardware implementation, is routinely used in light scattering experiments but has not yet found widespread use in computer simulations.

Analytical calculation of resonant inductance for zero voltage switching in phase-shifted full-bridge converters

The phase shift full bridge (PSFB) converter allows high efficiency power conversion at high frequencies through zero voltage switching (ZVS); the parasitic drain-to-source capacitance of the MOSFET is discharged by a resonant inductance before the switch is gated resulting in near zero turn-on switching losses. Typically, an extra inductance is added to the leakage inductance of a transformer to form the resonant inductance necessary to charge and discharge the parasitic capacitances of the PSFB converter. However, many PSFB models do not consider the effects of the magnetizing inductance or dead-time in selecting the resonant inductance required to achieve ZVS. The choice of resonant inductance is crucial to the ZVS operation of the PSFB converter. Incorrectly sized resonant inductance will not achieve ZVS or will limit the load regulation ability of the converter. This paper presents a unique and accurate equation for calculating the resonant inductance required to achieve ZVS over a wide load range incorporating the effects of the magnetizing inductance and dead-time. The derived equations are validated against PSPICE simulations of a PSFB converter and extensive hardware experimentations.

Efficient calculation of two-dimensional periodic and waveguide acoustic Green’s functions

New representations and efficient calculation methods are derived for the problem of propagation from an infinite regularly spaced array of coherent line sources above a homogeneous impedance plane, and for the Green's function for sound propagation in the canyon formed by two infinitely high, parallel rigid or sound soft walls and an impedance ground surface. The infinite sum of source contributions is replaced by a finite sum and the remainder is expressed as a Laplace-type integral. A pole subtraction technique is used to remove poles in the integrand which lie near the path of integration, obtaining a smooth integrand, more suitable for numerical integration, and a specific numerical integration method is proposed. Numerical experiments show highly accurate results across the frequency spectrum for a range of ground surface types. It is expected that the methods proposed will prove useful in boundary element modeling of noise propagation in canyon streets and in ducts, and for problems of scattering by periodic surfaces.

Approximate solution of second kind integral equations on infinite cylindrical surfaces

The paper considers second kind integral equations of the form $\phi (x) = g(x) + \int_S {k(x,y)} \phi (y)ds(y)$ (abbreviated $\phi = g + K\phi $), in which S is an infinite cylindrical surface of arbitrary smooth cross section. The “truncated equation” (abbreviated $\phi _a = E_a g + K_a \phi _a $), obtained by replacing S by $S_a $, a closed bounded surface of class $C^2 $, the boundary of a section of the interior of S of length $2a$, is also discussed. Conditions on k are obtained (in particular, implying that K commutes with the operation of translation in the direction of the cylinder axis) which ensure that $I - K$ is invertible, that $I - K_a $ is invertible and $(I - K_a )^{ - 1} $ is uniformly bounded for all sufficiently large a, and that $\phi _a $ converges to $\phi $ in an appropriate sense as $a \to \infty $. Uniform stability and convergence results for a piecewise constant boundary element collocation method for the truncated equations are also obtained. A boundary integral equation, which models three-dimensional acoustic scattering from an infinite rigid cylinder, illustrates the application of the above results to prove existence of solution (of the integral equation and the corresponding boundary value problem) and convergence of a particular collocation method.

Efficient calculation of the green function for acoustic propagation above a homogeneous impedance plane

This paper is concerned with the problem of propagation from a monofrequency coherent line source above a plane of homogeneous surface impedance. The solution of this problem occurs in the kernel of certain boundary integral equation formulations of acoustic propagation above an impedance boundary, and the discussion of the paper is motivated by this application. The paper starts by deriving representations, as Laplace-type integrals, of the solution and its first partial derivatives. The evaluation of these integral representations by Gauss-Laguerre quadrature is discussed, and theoretical bounds on the truncation error are obtained. Specific approximations are proposed which are shown to be accurate except in the very near field, for all angles of incidence and a wide range of values of surface impedance. The paper finishes with derivations of partial results and analogous Laplace-type integral representations for the case of a point source.

First-principles calculation of the AlAs/GaAs interface band structure using a self-energy-corrected local density approximation

We apply a self-energy-corrected local density approximation (LDA) to obtain corrected bulk band gaps and to study the band offsets of AlAs grown on GaAs (AlAs/GaAs). We also investigate the Al(x)Ga(1-x)As/GaAs alloy interface, commonly employed in band gap engineering. The calculations are fully ab initio, with no adjustable parameters or experimental input, and at a computational cost comparable to traditional LDA. Our results are in good agreement with experimental values and other theoretical studies. Copyright (C) EPLA, 2011