1,532 research outputs found
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 , , and
and two polarizabilities and , which
characterize a single water molecule and are deduced from single molecule data.Comment: 4 revtex pages, 3 embedded color PS figure
Heterotropic co-operative effects between amino acid substrates of phenylalanine hydroxylase
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
Failure of analysis of amino acid composition as a probe for sequence similarity in tetanus toxin
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
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