Effect of quantum nuclear motion on hydrogen bonding

This work considers how the properties of hydrogen bonded complexes, D-H....A, are modified by the quantum motion of the shared proton. Using a simple two-diabatic state model Hamiltonian, the analysis of the symmetric case, where the donor (D) and acceptor (A) have the same proton affinity, is carried out. For quantitative comparisons, a parametrization specific to the O-H....O complexes is used. The vibrational energy levels of the one-dimensional ground state adiabatic potential of the model are used to make quantitative comparisons with a vast body of condensed phase data, spanning a donor-acceptor separation (R) range of about 2.4-3.0 A, i.e., from strong to weak bonds. The position of the proton and its longitudinal vibrational frequency, along with the isotope effects in both are discussed. An analysis of the secondary geometric isotope effects, using a simple extension of the two-state model, yields an improved agreement of the predicted variation with R of frequency isotope effects. The role of the bending modes in also considered: their quantum effects compete with those of the stretching mode for certain ranges of H-bond strengths. In spite of the economy in the parametrization of the model used, it offers key insights into the defining features of H-bonds, and semi-quantitatively captures several experimental trends.Comment: 12 pages, 8 figures. Notation clarified. Revised figure including the effect of bending vibrations on secondary geometric isotope effect. Final version, accepted for publication in Journal of Chemical Physic

Sub-millimeter images of a dusty Kuiper belt around eta Corvi

We present sub-millimeter and mid-infrared images of the circumstellar disk around the nearby F2V star eta Corvi. The disk is resolved at 850um with a size of ~100AU. At 450um the emission is found to be extended at all position angles, with significant elongation along a position angle of 130+-10deg; at the highest resolution (9.3") this emission is resolved into two peaks which are to within the uncertainties offset symmetrically from the star at 100AU projected separation. Modeling the appearance of emission from a narrow ring in the sub-mm images shows the observed structure cannot be caused by an edge-on or face-on axisymmetric ring; the observations are consistent with a ring of radius 150+-20AU seen at 45+-25deg inclination. More face-on orientations are possible if the dust distribution includes two clumps similar to Vega; we show how such a clumpy structure could arise from the migration over 25Myr of a Neptune mass planet from 80-105AU. The inner 100AU of the system appears relatively empty of sub-mm emitting dust, indicating that this region may have been cleared by the formation of planets, but the disk emission spectrum shows that IRAS detected an additional hot component with a characteristic temperature of 370+-60K (implying a distance of 1-2AU). At 11.9um we found the emission to be unresolved with no background sources which could be contaminating the fluxes measured by IRAS. The age of this star is estimated to be ~1Gyr. It is very unusual for such an old main sequence star to exhibit significant mid-IR emission. The proximity of this source makes it a perfect candidate for further study from optical to mm wavelengths to determine the distribution of its dust.Comment: 22 pages, 4 figures. Scheduled for publication in ApJ 10 February 2005 issu

CO emission from discs around isolated HAeBe and Vega-excess stars

We describe results from a survey for J=3-2 12CO emission from visible stars with an infrared excess. The line is clearly detected in 21 objects, with molecular gas (>10^-3 Jupiter masses) common in targets with infrared excesses >0.01 (>56% of objects). Such high excesses indicate the presence of a disc of opening angle >12 degrees; within this, the optically thick disc prevents CO photodissociation. Two or three stars with associated CO have an excess <0.01, implying a disc opening angle <1 degree. Most line profiles are double-peaked or relatively broad. Model fits, assuming a Keplerian disc, indicate outer radii, R_out, of ~20-300 au. As many as 5 discs have outer radii smaller than the Solar System (50 au), and a further 4 have gas at radii <20 au. R_out is independent of the stellar spectral type (from K through to B9), but is correlated with total dust mass. R_out appears to decrease with time: discs around stars of age 3-7 Myr have a mean radius of ~210 au, whereas discs of age 7-20 Myr are a factor of 3 smaller. The only bona fide debris disc with detected CO is HD9672; this has a double peaked line profile and is the most compact gas disc observed, with a modelled radius 17 au). A fit to HD141569 suggests the gas lies in two rings of radii 90 and 250 au, similar to the scattered light structure. In both AB Aur and HD163296 the sizes of the molecular and dust scattering discs are also similar, suggesting that the gas and small dust grains are co-located.Comment: 16 pages, 5 figures MNRAS - accepte

Polarization forces in water deduced from single molecule data

Intermolecular polarization interactions in water are determined using a minimal atomic multipole model constructed with distributed polarizabilities. Hydrogen bonding and other properties of water-water interactions are reproduced to fine detail by only three multipoles $\mu_H$, $\mu_O$, and $\theta_O$ and two polarizabilities $\alpha_O$ and $\alpha_H$, which characterize a single water molecule and are deduced from single molecule data.Comment: 4 revtex pages, 3 embedded color PS figure

The Doppler Peaks from Cosmic Texture

We compute the angular power spectrum of temperature anisotropies on the microwave sky in the cosmic texture theory, with standard recombination assumed. The spectrum shows `Doppler' peaks analogous to those in scenarios based on primordial adiabatic fluctuations such as `standard CDM', but at quite different angular scales. There appear to be excellent prospects for using this as a discriminant between inflationary and cosmic defect theories.Comment: 14 pages, latex, 3 figures, compressed and uuencoded, replaced version has minor typographical correction

Spectropolarimetric observations of Herbig Ae/Be Stars I: HiVIS spectropolarimetric calibration and reduction techniques

Using the HiVIS spectropolarimeter built for the Haleakala 3.7m AEOS telescope in Hawaii, we are collecting a large number of high precision spectropolarimetrc observations of stars. In order to precisely measure very small polarization changes, we have performed a number of polarization calibration techniques on the AEOS telescope and HiVIS spectrograph. We have extended our dedicated IDL reduction package and have performed some hardware upgrades to the instrument. We have also used the ESPaDOnS spectropolarimeter on CFHT to verify the HiVIS results with back-to-back observations of MWC 361 and HD163296. Comparision of this and other HiVIS data with stellar observations from the ISIS and WW spectropolarimeters in the literature further shows the usefulness of this instrument.Comment: 35 pages, 44 figures, Accepted by PAS

Fundamental parameters of Cepheids. V. Additional photometry and radial velocity for southern Cepheids

I present photometric and radial velocity data for Galactic Cepheids, most of them being in the southern hemisphere. There are 1250 Geneva 7-color photometric measurements for 62 Cepheids, the average uncertainty per measurement is better than 0.01 mag. A total of 832 velocity measurements have been obtained with the CORAVEL radial velocity spectrograph for 46 Cepheids. The average accuracy of the radial velocity data is 0.38 km/s. There are 33 stars with both photometry and radial velocity data. I discuss the possible binarity or period change that these new data reveal. I also present reddenings for all Cepheids with photometry. The data are available electronically.Comment: To appear in ApJS. Data available electronically at ftp://cfa-ftp.harvard.edu/pub/dbersier

Charge Transfer in Partition Theory

The recently proposed Partition Theory (PT) [J.Phys.Chem.A 111, 2229 (2007)] is illustrated on a simple one-dimensional model of a heteronuclear diatomic molecule. It is shown that a sharp definition for the charge of molecular fragments emerges from PT, and that the ensuing population analysis can be used to study how charge redistributes during dissociation and the implications of that redistribution for the dipole moment. Interpreting small differences between the isolated parts' ionization potentials as due to environmental inhomogeneities, we gain insight into how electron localization takes place in H2+ as the molecule dissociates. Furthermore, by studying the preservation of the shapes of the parts as different parameters of the model are varied, we address the issue of transferability of the parts. We find good transferability within the chemically meaningful parameter regime, raising hopes that PT will prove useful in chemical applications.Comment: 12 pages, 16 figure