Vibration-rotation bands in ethane

The absorption spectrum of ethane was recorded at 0.014 cm^?1 resolution in the range 4500–6500 cm^?1 using a Fourier transform spectrometer and at room temperature. Eighteen bands could be identified and their type assigned. Upper state rotational constants are provided for the band at 5948.338 cm^?1 and Coriolis constants are obtained for most perpendicular bands. Vibrational assignments are suggested for the bands at 5948 cm^?1 (v7 + v10), 5914 cm^?1(v8 + v ₁₀+ v ₁₁), and 5852cm^?1 (v ₅+v ₁₀). All vibrational bands reported in the literature are gathered.     

A chemical potential equalization model for treating polarization in molecular mechanical force fields

Molecular mechanical force fields are widely used in molecular simulation studies due to their simplicity and efficiency. Although accurate enough for many purposes, force fields are approximations and neglect several effects that are important at an atomic level. Probably the most significant of these, that is not taken into account by the majority of force fields, is the ability of the charge distribution of a molecule to polarize in response to changes in its environment. There are several ways of including polarization effects in force fields but, in this paper, we investigate a relatively new approach, called the chemical potential equalization model, which is based upon the principle of electronegativity equalization and which is a generalization of the class of fluctuating charge models. We detail the principles behind the model and of our implementation of it and then present parametrizations of the model for the molecules, methane and water, and the chloride anion. Gas- and solution-phase calculations to test the parametrizations indicate that the model gives results that are in good agreement with experiment and that compare well to those obtained with non-polarizable force fields and other polarizable models.     

A Computer Program to Calculate the Percent Total Deuteration in an Exchange Reaction

The acid-catalyzed hydrogen-deuterium exchange reaction in aliphatic ketones was modeled as a purely random process. Using a computer program, a statistically random hydrogen-deuterium exchange was simulated for a particular molecule, 2-indanone. For this molecule, there are two carbons, each providing two potential sites for exchange. The program determined the relative amounts for each of the partially deuterated species, including the total percent deuteration. A comparison with mass spectral data showed good agreement with this model.     

Einstein Metrics with Nonpositive Sectional Curvature on Extensions of Lie Algebras of Heisenberg Type

The purpose of this article is to study some simply connected Lie groups with left invariant Einstein metric, negative Einstein constant and nonpositive sectional curvature. These Lie groups are classified if their associated metric Lie algebra s is of Iwasawa type and s = An₁n₂...n_r, where all n_iare Lie algebras of Heisenberg type with [[n_i,n_j] = {0} for ij. The most important ideas of the article are based on a construction method for Einstein spaces introduced by Wolter in 1991. By this method some new examples of Einstein spaces with nonpositive curvature are constructed. In another part of the article it is shown that Damek-Ricci spaces have negative sectional curvature if and only if they are symmetric spaces.     

Asymptotic approximations for functions defined by series, with some applications to the theory of guided waves

Mellin transforms are used here to find asymptotic approximationsfor functions defined by series. The simplest cases are thoseof the form _–1;u(nx). Such series are called separablehere, because the given function u is sampled at points whosevariation with n and x is separated. Nonseparable series areanalysed by first approximating them by separable series. Bothtypes of series arise in the theory of electromagnetic waveguidesand in the theory of linear water waves; several examples areworked out in detail.     

ON THE MECHANISM OF QUENCHING OF SINGLET OXYGEN BY AMINES-III. EVIDENCE FOR A CHARGE-TRANSFER-LIKE COMPLEX

Abstract— A series of amines were found to quench singlet oxygen in the order tertiary > secondary > primary, with a reasonable correlation between the log of their rate constant of quenching and their ionization potential. In addition, a Hammett rho plot gave a rho value of - 1.39 for the quenching of singlet oxygen by a series of substituted N, N-dimethylanilines, in good agreement with the results obtained by a different method. It was found that some of the amines (anilines) quenched the triplet state of the dye-sensitizer (Rose Bengal) used for the production of singlet oxygen. Corrections in the results were made in the calculations of rates of quenching of singlet oxygen to allow for the triplet-state quenching. No extensive quenching of the singlet state of the dye was observed at the concentrations of the amines necessary for singlet-oxygen quenching. In one case (N, N, N', N'-tetramethylphenylenediamine) there was no observable chemical reaction between singlet oxygen and the amine. It was concluded that singlet oxygen undergoes physical quenching by the amines via partial charge-transfer intermediates.     

Spectroscopy and dynamics of the isolated sp2 CH chromophore in trideuteroacetaldehyde CD3CHO as derived from extrapolated SDCI ab initio calculations

Ab initio CI potential energy (PES) and dipole moment (DMS) surfaces have been calculated with singles and doubles excitation configuration interaction (SDCI) for the 2-dimensional isolated sp² CH chromophore subspace of trideuteroacetaldehyde (CD₃CHO). Different extrapolation schemes to full-CI have been applied after the extrapolation to full-SDCI. Vibrational band centres and absolute intensities are determined variationally on six extrapolated surfaces. The band centres are analysed within the effective Hamiltonian model for isolated CH chromophores and the effective spectroscopic parameters are compared for the different extrapolation schemes. Time dependent population evolution for vibrational quantum motion with a pure CH stretching state being initially populated is calculated for some of the extrapolated surfaces within the effective Hamiltonian model.