Conformational analysis of some dimethylheptanes with the aid of normal coordinate calculations

Infrared spectra were obtained for the series of 2,X-dimethylheptanes (X = 2,3,4,5,6) and were interpreted with the aid of normal coordinate calculations. 2,2-DMH exists as two conformers, with the C_s conformer being the only one present in the crystalline solid. 2,3-DMH exists in at least three conformations, all of C₁ symmetry. Ambiguities in spectral data indicate that more conformations are present. Two C₁ conformations of 2,4-DMH were shown to be present, but an unassigned band may indicate the presence of a third conformer. The presence of at least four conformers, all of C₁ symmetry, was shown to be necessary to explain the spectrum of 2,5-DMH. Finally, 2,6-DMH was shown to exist as three conformers, of symmetries C_s, C₂, and C₁. Vibrational assignments were made for all the probable conformers of all five compounds.     

Vibrational analysis of 1,4-dibromopentane

Infrared and Raman spectra have been obtained for 1,4-dibromopentane and interpreted with the aid of normal coordinate calculations. It is concluded that all six conformers resulting from rotation about the C₁-C₂ and C₃-C₄ bonds probably exist in the neat liquid and amorphous solid, and that the compound crystallizes in the P_HS_HH conformer that has the two bromine atoms on opposite sides of the plane of carbon atoms. The compound therefore behaves like 1,3-dibromopropane and 1,4-dibromobutane.     

Vibrational spectra and conformational behavior of benzyl fluoride

Infrared and Raman spectra have been obtained for benzyl fluoride and a vibrational assignment has been made. The spectra indicate the presence of a large number of conformers that differ only in the orientation of the C-F bond, as a result of free or nearly free internal rotation.     

Force constants and normal vibrations of the haloacetonitriles

Normal coordinate calculations were carried out for fluoro-, chloro-, bromo- and iodoacetonitrile, using a seventeen-parameter valence force field. Most of the force constants have different values in the four halides that change in a regular manner. The a″ vibrations are essentially pure, but there is considerable mixing of normal modes in the a′ species. The difference in previous vibrational assignments is resolved but the bands assigned to the C-C-Br and C-C-I bends were found to be mainly C-Br and C-I stretching vibrations. Transferability of the force constants obtained for the CH₂Cl group seems quite good.     

Longitudinal-transverse separations of deep-inelastic structure functions at low Q2 for hydrogen and deuterium

We report on a study of the longitudinal to transverse cross section ratio, R=sigmaL/sigmaT, at low values of x and Q2, as determined from inclusive inelastic electron-hydrogen and electron-deuterium scattering data from Jefferson Laboratory Hall C spanning the four-momentum transfer range 0.06相似文献   

Likelihood-ratio changepoint features for consumer-behaviour models

Some predictive models for customer value management might benefit from information about certain changes in individual-consumer behaviour. We take changepoint methods as the first step in producing a model-input feature for this purpose. An unusual feature in the application of changepoint methods to consumer data is there are as many streams of data as there are customers. This property is used to help decide whether an individual has changed their behaviour by ordering likelihood-ratio statistics from the changepoint models. Following a review of changepoint methods, the approach is demonstrated on cash machine transactions. Models for the amount, location and time of transaction are used and accounts exhibiting large evidence of change are examined in detail. For the data set used the approach performs sensibly. The worth of likelihood-ratio statistics to rank evidence for change is considered more generally through some of the literature.     

Normal Coordinate Analysis of 3-Bromo-1,3-Dinitroazetidine

Abstract

The infrared spectrum of 3-bromo-1,3-dinitroazetidine was interpreted with the aid of normal coordinate calculations. A seventy-two parameter modified valence field was used in those calculations, and the observed wave numbers were fit with an average error of 2.5 cm^?1. An assignment of the bands in terms of symmetry coordinates is given. Many of the force constants were transferred to 1-acetyl-3,3-dinitroazetidine to aid in normal coordinate calculations for that compound.     

Conformational Analysis of Some Dichloroalkanes

Molecular mechanics calculations were made for 1,1-dichlorobutane, 2,2-dichlorobutane, and 1,2-dichloro-2-methylpropane in order to compare the results with conclusions obtained from vibrational spectra concerning the conformational behavior of these compounds. Calculations were also made for 1,2-dichloro-2-methylbutane, although vibrational spectra are not available for this compound. The structures and relative energies of the most abundant conformers are given.     

Validation of subgradient optimization

The “relaxation” procedure introduced by Held and Karp for approximately solving a large linear programming problem related to the traveling-salesman problem is refined and studied experimentally on several classes of specially structured large-scale linear programming problems, and results on the use of the procedure for obtaining exact solutions are given. It is concluded that the method shows promise for large-scale linear programming