Force field calculation for inplane vibrations of ethylene usingcndo/Force method

cndo/Force method is used to evaluate redundancy-free internal valence force field (rfivff) for inplane vibrations of ethylene. The bending force constants, the stretch-band and bend-bend interaction force constants are predicted reasonably well in magnitude and sign by this method; whereas stretching force constants and stretch-stretch interactions are overestimated. Initial force field is set up by transferring stretching force constants from structurally-related molecules and including the rest of the force constants fromcndo force field. The field so constructed is subjected to refinement by the least square method. A total of 64 vibrational frequencies of C₂H₄, C₂D₄, C₂H₂D₂ and their¹³C isotopic modifications are used to determine force field containing 15 parameters. The final force field is found to be reasonable on the basis of frequency fits, potential energy distribution and band assignments.     

Raman Spectrum of Crystalline Pyrimidine

In an earlier work¹we have investigated an oriented crystal of pyrimidine at liquid nitrogen temperature using polarized infrared radiation. The static field effect for an A₂ mode (16a) and correlation field splitting for fourteen fundamentals have been observed¹. This paper reports the Raman spectrum of crystalline pyrimidine at liquid nitrogen temperature.     

Force field calculations of acetonitrile using CNDO/force method

The redundancy-free internal valence force field (RFIVFF) of acetonitrile is reported using CNDO/force method. The initial force field is set up by taking the interaction and bending force constants from CNDO force field and transferring stretching force constants from the force fields of chemically related molecules. The final force field is obtained by refining the initial force field using vibrational harmonic frequencies of CH₃CN,¹³CH₃CN, CH₃ ¹³CN, CH₃C¹⁵N, CD₃CN and CD₃ ¹³CN. The final force field thus obtained is found to be excellent on the basis of frequency fit and potential energy distribution.     

Vibrational Spectroscopic and Theoretical Studies of Urea Derivatives with Biochemical Interest: N,N′-Dimethylurea,N,N,N′,N′-Tetramethylurea,and N,N′-Dimethylpropyleneurea

Abstract

Mid-infrared, far-infrared, and Raman vibrational spectroscopic studies were combined with density functional theory (DFT) calculations and normal coordinate force field analyses for N,N′-dimethylurea (DMU), N,N,N′,N′-tetramethylurea (TMU), and N,N′-dimethylpropyleneurea (DMPU: IUPAC name 1,3-dimethyltetrahydropyrimidin-2(1H)-one). The equilibrium molecular geometry of DMU (all three conformers), TMU, and DMPU and the frequencies, intensities, and depolarization ratios of their fundamental infrared (IR) and Raman vibrational transitions were obtained by DFT calculations. The vibrational spectra were fully analyzed by normal coordinate methods as well. A starting force field for DMPU was obtained by adapting corresponding force constants for DMU and TMU, resulting after refinements in the stretching force constants C=O (7.69, 7.30, 7.68 N·cm^?1), C–N (5.16, 5.55, 5.05 N·cm^?1), and C-Me (5.93, 4.00, 4.22 N·cm^?1) for DMU, TMU, and DMPU, respectively. The dominating conformer of liquid DMU was identified as trans-trans, strong intermolecular hydrogen bonding was verified in solid DMU, and weak dipole–dipole association was found in liquid TMU and in DMPU. Special attention was paid to analyzing the methyl group frequencies, which revealed deviations from local C_3v symmetry. A linear correlation was found between the CH stretching force constants and the inverse of the CH bond lengths (1/r ²). The averaged NH stretching frequencies of gaseous, dissolved, and solid urea and of DMU, with variations for hydrogen bonding of different strength, are linearly correlated to the NH stretching force constants. Characteristic skeletal vibrations were assigned for a broad variety of urea derivatives and also for pyrimidine derivatives, which all contain the N₂C=O entity. The very strong IR bands of C=O stretching (1,676 ± 40 cm^?1) and asymmetric CN₂ stretching (1,478 ± 60 cm^?1), and the very intense Raman feature of symmetric CN₂ stretching or ring breathing (757 ± 80 cm^?1), can be recognized as fingerprint bands also for the pyrimidine derivatives cytosine, thymine, and uracil, which all are nucleobases in DNA and RNA nucleotides.     

Determination of force fields for two conformers of nitromethane bycndo/Force method

cndo/Force method is used to evaluate the redundancy free internal valence force fields for two conformers of nitromethane. The initial force field is set up by taking the interaction and bending force constants from this method and transferring the stretching force constants from the force fields of chemically related molecules. The final force field is obtained by refining the initial force field using vibrational frequencies of isotopic speciesviz CH₃NO₂, CD₃NO₂, CH₃ ¹⁵NO₂ and CH₃N¹⁸O₂. The final force field thus obtained is reasonable on the basis of frequency fit and potential energy distribution. The barrier to internal rotation is found to be 0.048 kcal mol⁻¹.     

Calculation of the Normal Vibrations of Benzene in the First Singlet Electron-Excited State 1 B 2u

Using the CIS/6-311+G^** method, the normal vibrations of the benzene molecule in the first singlet electron-excited state ¹ B _2u have been calculated. The algorithm of calculation of the force field in dependent coordinates by the method of generalized inversion is described. A method of autoscaling in dependent natural coordinates is suggested. For six groups of natural coordinates scaling factors have been obtained, the use of which has led to agreement between the calculated and experimental frequencies of the vibrations of benzene. The frequencies of the B _1u -symmetry-type vibrations, for which there is no experimental assignment, have been calculated. The problem of selection of the force field in dependent coordinates is discussed.     

Modeling of vibrational energy levels of methane from the Ab initio constructed potential energy surface

The potential energy surface of the methane molecule in the ground electronic state is ab initio constructed. The CCSD(T) method with the cc-pVQZ basis set is used to calculate the potential energy at 18982 points. The obtained set of points makes it possible to determine the force field up to the tenth order. The modified Gray-Robiette coordinates were used for the construction of the analytical form of the surface. Vibrational energy levels for ¹²CH₄ were calculated up to 6200 cm^?1. Calculations performed are compared with experiment and other calculations.     

Vibrational Behaviour of the CrO3- 4 Anion in Different Crystalline Environments

The powder-infrared spectra of different crystalline compounds containing the tetrahedral Cro^3- ₄, anion have been recorded and analyzed with the aid of the site symmetry rules. In some cases Raman data are also reported. The effect of the different crystalline environments is discussed in detail and comparisons with isostructural phases are also made. A definitive assignment for the internal vibrations of the CrO^3- ₄, ion is proposed and a new set of force constants has been calculated fron a modified valence force field.     

On the calculation of steady-state magnetohydrodynamic flows of liquid metals in circular ducts of a rectangular cross section

A numerical code has been designed to calculate two-dimensional steady-state magnetohydrodynamic (MHD) flows of incompressible conducting fluids (liquid metals) in linear and circular thin-wall ducts of a rectangular cross section. The flows are caused by the Lorentz force J × B that appears when an electric current passes through a fluid placed in a vertical uniform magnetic field. The code is the generalization of the well-known iteration Gauss-Seidel method to the case of a set of elliptical equations. The method proposed can be used to calculate steady-state flows over wide ranges of Hartmann (Ha = 1–10³) and Reynolds (Re = 1–10⁶) numbers.     

Influence of gravity on the solidification of eutectics I. theory

In the frame of a simple model, the paper presents a theoretical analysis of the influence of an external force field (gravity) on the solidification of an eutectic complex-forming melt. It is shown in terms of the so-called singular perturbation method that —in contrast to classical theories of freezing — the direct influence of the gravitational field cannot be neglected in such a solidifying melt in which nonlinear processes take place. Under standard (i.e. g₀= 9·81 m s^–2) and zero gravity conditions, the differences in undercoolings and lamellar spacings are determined analytically.     

The anharmonic force field and equilibrium structure of methane

The anharmonic force field of methane has been refined to fit spectroscopic data from the isotopic species ¹²CH₄, ¹³CH₄, ¹²CH₄, ¹²CH₃D, ¹²CHD₃ and ¹²CH₂D₂. Six of the thirteen cubic force constants have been determined experimentally, the remaining cubic constants being fixed at values derived from ab initio calculations. The quartic force field is very crude, in that only f_rrrr has been refined. It is concluded however that the cubic and quartic force fields, even though they are subject to limitations, provide a considerable improvement in the experimental determination of the r _e structure and the quadratic force field. The equilibrium bond length is found to be r _e(CH) = 1·085₈ ± 0·001 Å.     

The effect of a gravitational induction force on the stellar orbits in galaxies

This paper explores the effect of a gravitational induction force, similar to gravito-electromagnetism but of several orders of magnitude larger, on a spiral galaxy. This would provide, because of the huge amount of mass currents associated with spirals, a rather large gravitational induction force. Standard gravitational dynamics is modified by adding an anti-symmetric force tensor analogous to electromagnetism. By choosing a special free space solution to the Einstein field equations, it was found that the resulting force field would drop off by an r ⁻¹ rather than an r ⁻² rule. Thus this new induction force would grow to dominance over the large distances associated with galaxies. Any r ⁻¹ force will produce the flat rotation curves that are observed in disk galaxies as well as explain the Tully-Fisher relationship. It would also explain why the inner core of the spirals remain Newtonian. Quite surprisingly, this simple hypothesis also seems to offer explanations for many other observed phenomena as well.     

Possible measurement of the gravitational acceleration of antiprotons in the presence of “strong” patch effect electrical fields

The role of electrical fields due to the patch effect in a Penning trap used to measure the Earth's gravitational accelerationg on antiprotons is analyzed. Theg measurement method is based on the study of the gravity-induced shift of the center of the radial orbits of particles stored in a Penning trap having the magnetic field perpendicular to the direction of the force of gravity. The analysis of the radial motion shows that forces originating from patch effect electrical fields about ten times stronger than the force of gravity, still allow a differential measurement ofg for antiprotons and matter particles (H^–). As the precision of the measurement is affected by the particle axial energy distribution, particular care must be devoted to injecting antiprotons and H^– ions into the trap with very similar initial conditions.     

Direct study of the lifetime and acceleration of a coloured nucleon

We propose a method of studying directly the confinement part of the force due to the coloured field, and the time that a coloured hadron remains coloured. Applying the method topp→pX data we find that the mean time for colour neutralization of a coloured nucleon is 1.2±0.1 fm/c or (3.9±0.3)×10^?24 s.     

小变形原子核中的相干效应

本文考察了在转动的小变形核力场中运动的核子-核子对、核子-空穴对中的相干效应。计算了O¹⁸最低的偶宇称态0⁺,2⁺,4⁺和O¹⁶最低的奇宇称态0^-,1^-,2^-,3^-波函数;和壳模型经典方法计算出的结果作了比较,二者相当一致。得出的初步结论如下:核力主要是P₂力再加上一定成分具有相干性质的力。前者与转动的变形场等效。不但对于0⁺,2⁺,4⁺,3^-态,而且对于1^-,2^-态,附加的相干成分都很重要;它们的内部态混合组态是比较多的,粒子-粒子之间、或粒子-空穴之间的关联都比较显著。只有0^-态的内部态是纯组态。     

Measuring the gravitational acceleration of antimatter with an antihydrogen interferometer

The gravitational force on antimatter has never been directly measured. A method is suggested for making this measurement by directing a low-energy beam of neutral antihydrogen atoms through a transmission-grating interferometer and measuring the gravitationally-induced phase shift in the interference pattern. A 1% measurement of the acceleration due to the Earth's gravitational field (¯ g) should be possible from a beam of about 10⁵ or 10⁶ atoms. If more antihydrogen can be made, a much more precise measurement of¯ g would be possible. A method is suggested for producing an antihydrogen beam appropriate for this experiment.     

Sextic force field of nitrous oxide

The sextic force field in the curvilinear internal coordinates has been studied for the nitrous oxide molecule from the spectroscopic data of ¹⁴N₂¹⁶O, ¹⁴N¹⁵N¹⁶O, and ¹⁵N¹⁴N¹⁶O. The bands below 6600 cm⁻¹ have been used. The force constants in the internal coordinates are converted to those in dimensionless normal coordinates by two successive transformations. The vibration Hamiltonian matrix for each symmetry species of a given isotopic species has been constructed from the harmonic oscillator basis functions, and it is then diagonalized numerically to give the vibrational energy levels and the wavefunctions. The latter have been used for the evaluation of ratational constants. The least-squares refinement has been very successful in the present study, and it is shown that the general quartic force field supplemented by the quintic and sextic stretching diagonal force constants estimated from the Morse function, provided that the terms up to sextic are kept in the dimensionless normal coordinate space, well reproduces the spectroscopic constants such as the vibrational levels, rotational constants, l-type doubling constants, and centrifugal distortion constants. The spectroscopic constants of the isotopic molecules which are excluded from the refinement process are also in good agreement with the computed ones. The bond dissociation energies of the NN and NO bonds estimated from the present results have been critically examined.     

An extended ab initio study of the rotation-vibration spectrum of HOC+

Configuration interaction calculations have been performed in order to investigate the bending potential of the molecular ion HOC⁺ in detail. It is found that the bending potential has its minimum at the linear configuration and that it is very shallow. The ab initio points on the electronic ground state surface of HOC⁺ were combined with previously calculated points to determine an improved force field. This force field was used in the second-order rotation-vibration perturbation Hamiltonian, as well as in the semirigid bender Hamiltonian, to evaluate rotation and vibration frequencies of HOC⁺ and of some of its isotopes. The ν₀(J = 1?0) rotational transition frequency of the DOC⁺ isotope is predicted to be 76 200 ± 40 MHz.