Restricted rotation dynamics and far-infrared spectra of liquid water governed by elastic interactions

A semi-phenomenological model describing wideband dielectric and far-infrared spectra of liquid water was proposed recently by the same authors [J. Mol. Struct. 606 (2002) 9], where a small dipole-moment component changing harmonically with time determines a weak absorption band (termed here the R-band) centred at the wavenumber v similar to 200 cm(-1). In the present work, a rough molecular theory of the R-band based on the concept of elastic interactions is given. Stretching and bending of hydrogen bonds cause restricted rotation (RR) of a polar water molecule in terms of a dimer comprising the H- bonded molecules. Analytical expression for the RR frequency nu(str) is derived as a function of the RR amplitude, geometrical parameters and force constants. The density g(nu(str)) of frequency distribution is shown to be centred in the R-band. The spectrum of the dipolar auto-correlation function calculated for this structural-dynamical model is found. A composite model comprising two intermolecular potentials is proposed, which yields for water a good description of the experimental wideband (from 0 to 1000 cm(- 1)) spectra of complex permittivity and of absorption coefficient. The presented interpretation of these spectra is based on a concept that water presents a two-component solution, with components differing by the types of molecular rotation. (C) 2003 Elsevier B.V. All rights reserved.

Non-radial pulsation, rotation and outburst in the Be star omega Orionis from the MuSiCoS 1998 campaign

omega Ori (HD37490, HR1934) is a Be star known to have presented variations. In order to investigate the nature and origin of its short-term and mid-term variability, a study is performed of several spectral lines (Halpha, Hdelta, HeI 4471, 4713, 4921, 5876, 6678, CII 4267, 6578, 6583, Mg II 4481, Si III 4553 and Si II 6347), based on 249 high signal-to-noise high-resolution spectra taken with 8 telescopes over 22 consecutive nights during the MuSiCoS (Multi SIte COntinuous Spectroscopy) campaign in November-December 1998. The stellar parameters are revisited and the projected rotational velocity (v sin i = 179 km s(-1)) is redetermined using several methods. With the MuSiCoS 98 dataset, a time series analysis of line-profile variations (LPVs) is performed using the Restricted Local Cleanest (RLC) algorithm and a least squares method. The behaviour of the velocity of the centroid of the lines, the equivalent widths and the apparent vsini for several lines, as well as Violet and Red components of photospheric lines affected by emission (red He i lines, Si II 6347, CII 6578, 6583) are analyzed. The non-radial pulsation (NRP) model is examined using phase diagrams and the Fourier-Doppler Imaging (FDI) method. The LPVs are consistent with a NRP mode with l = 2 or 3, \m\ = 2 with frequency 1.03 cd(-1). It is shown that an emission line outburst occurred in the middle of the campaign. Two scenarios are proposed to explain the behaviour of a dense cloud, temporarily orbiting around the star with a frequency 0.46 c d(-1), in relation to the outburst.

Photometry of cometary nuclei: Rotation rates, colours and a comparison with Kuiper Belt Objects

We present time-series data on Jupiter Family Comets (JFCs) 17P/Holmes, 47P/Ashbrook-Jackson and 137P/Shoemaker-Levy 2. In addition we also present results from `snap-shot' observations of comets 43P/Wolf-Harrington, 44P/Reinmuth 2, 103P/Hartley 2 and 104P/Kowal 2 taken during the same run. The comets were at heliocentric distances of between 3 and 7 au at this time. We present measurements of size and activity levels for the snap-shot targets. The time-series data allow us to constrain rotation periods and shapes, and thus bulk densities. We also measure colour indices (V - R) and (R - I) and reliable radii for these comets. We compare all of our findings to date with similar results for other comets and Kuiper Belt Objects (KBOs). We find that the rotational properties of nuclei and KBOs are very similar, that there is evidence for a cut-off in bulk densities at ~0.6 g cm-3 in both populations, and the colours of the two populations show similar correlations. For JFCs, there is no observational evidence for the optical colours being dependent on either position in the orbit or orbital parameters.

The VLT-FLAMES survey of massive stars: mass loss and rotation of early-type stars in the SMC

We have studied the optical spectra of a sample of 31 O- and early B-type stars in the Small Magellanic Cloud, 21 of which are associated with the young massive cluster NGC 346. Stellar parameters are determined using an automated fitting method (Mokiem et al. 2005, A&A, 441, 711), which combines the stellar atmosphere code FASTWIND (Puls et al. 2005, A&A, 435, 669) with the genetic algorithm based optimisation routine PIKAIA (Charbonneau 1995, ApJS, 101, 309). Comparison with predictions of stellar evolution that account for stellar rotation does not result in a unique age, though most stars are best represented by an age of 1-3 Myr. The automated method allows for a detailed determination of the projected rotational velocities. The present day v(r) sin i distribution of the 21 dwarf stars in our sample is consistent with an underlying rotational velocity (v(r)) distribution that can be characterised by a mean velocity of about 160-190 km s(-1) and an effective half width of 100-150 km s(-1). The vr distribution must include a small percentage of slowly rotating stars. If predictions of the time evolution of the equatorial velocity for massive stars within the environment of the SMC are correct (Maeder & Meynet 2001, A&A, 373, 555), the young age of the cluster implies that this underlying distribution is representative for the initial rotational velocity distribution. The location in the Hertzsprung-Russell diagram of the stars showing helium enrichment is in qualitative agreement with evolutionary tracks accounting for rotation, but not for those ignoring vr. The mass loss rates of the SMC objects having luminosities of log L-star/L-circle dot greater than or similar to 5.4 are in excellent agreement with predictions by Vink et al. (2001, A&A, 369, 574). However, for lower luminosity stars the winds are too weak to determine. M accurately from the optical spectrum. Three targets were classified as Vz stars, two of which are located close to the theoretical zero-age main sequence. Three lower luminosity targets that were not classified as Vz stars are also found to lie near the ZAMS. We argue that this is related to a temperature effect inhibiting cooler from displaying the spectral features required for the Vz luminosity class.

High-resolution crystal structure of the intramolecular d(TpA) thymine-adenine photoadduct and its mechanistic implications.

A high-resolution crystal structure is reported for d(TpA)*, the intramolecular thymine–adenine photoadduct that is produced by direct ultraviolet excitation of the dinucleoside monophosphate d(TpA). It confirms the presence of a central 1,3-diazacyclooctatriene ring linking the remnants of the T and A bases, as previously deduced from heteronuclear NMR measurements by Zhao et al. (The structure of d(TpA)*, the major photoproduct of thymidylyl-(3'-5')-deoxyadenosine. Nucleic Acids Res., 1996, 24, 1554–1560). Within the crystal, the d(TpA)* molecules exist as zwitterions with a protonated amidine fragment of the eight-membered ring neutralizing the charge of the internucleotide phosphate monoanion. The absolute configuration at the original thymine C5 and C6 atoms is determined as 5S,6R. This is consistent with d(TpA)* arising by valence isomerization of a precursor cyclobutane photoproduct with cis–syn stereochemistry that is generated by [2 + 2] photoaddition of the thymine 5,6-double bond across the C6 and C5 positions of adenine. This mode of photoaddition should be favoured by the stacked conformation of adjacent T and A bases in B-form DNA. It is probable that the primary photoreaction is mechanistically analogous to pyrimidine dimerization despite having a much lower quantum yield.