23 research outputs found
Electric Dipole Moments from Stark Effect in Supersonic Expansion: n-Propanol, n-Butanol, and n-Butyl Cyanide
The orientation and magnitude of the molecular electric dipole moment are key properties relevant to topics ranging from the nature of intermolecular interactions to the quantitative analysis of complex gas-phase mixtures, such as chemistry in astrophysical environments. Stark effect measurements on rotational spectra have been the method of choice for isolated molecules but have become less common with the practical disappearance of Stark modulation spectrometers. Their role has been taken over by supersonic expansion measurements within a Fabry-Perot resonator cavity, which introduces specific technical problems that need to be overcome. Several of the adopted solutions are described and compared. Presently, we report precise electric dipole moment determinations for the two most stable conformers of the selected molecules of confirmed or potential astrophysical relevance: n-propanol, n-butanol, and n-butyl cyanide. All dipole moment components have been precisely determined at supersonic expansion conditions by employing specially designed Stark electrodes and a computer program for fitting the measured Stark shifts, inclusive of cases with resolved nuclear quadrupole hyperfine structure. The experimental values are compared with suitable quantum chemistry computations. It is found that, among the tested levels of computation, vibrationally averaged dipole moments are the closest to the observation and the molecular values are, as in the lighter molecules in the series, largely determined by the hydroxyl or nitrile groups
Correlations between short- and long-time relaxation in colloidal supercooled liquids and glasses
Spatiotemporal dynamics of short- and long-time structural relaxation are measured experimentally as a function of packing fraction, φ, in quasi-two-dimensional colloidal supercooled liquids and glasses. The relaxation times associated with long-time dynamic heterogeneity and short-time intracage motion are found to be strongly correlated and to grow by orders of magnitude with increasing φ toward dynamic arrest. We find that clusters of fast particles on the two timescales often overlap, and, interestingly, the distribution of minimum-spatial-separation between closest nonoverlapping clusters across the two timescales is revealed to be exponential with a decay length that increases with φ. In total, the experimental observations suggest short-time relaxation events are very often precursors to heterogeneous relaxation at longer timescales in glassy materials
Forced motion of a probe particle near the colloidal glass transition
We use confocal microscopy to study the motion of a magnetic bead in a dense
colloidal suspension, near the colloidal glass transition volume fraction
. For dense liquid-like samples near , below a threshold force
the magnetic bead exhibits only localized caged motion. Above this force, the
bead is pulled with a fluctuating velocity. The relationship between force and
velocity becomes increasingly nonlinear as is approached. The
threshold force and nonlinear drag force vary strongly with the volume
fraction, while the velocity fluctuations do not change near the transition.Comment: 7 pages, 4 figures revised version, accepted for publication in
Europhysics Letter
Mobility and Diffusion of a Tagged Particle in a Driven Colloidal Suspension
We study numerically the influence of density and strain rate on the
diffusion and mobility of a single tagged particle in a sheared colloidal
suspension. We determine independently the time-dependent velocity
autocorrelation functions and, through a novel method, the response functions
with respect to a small force. While both the diffusion coefficient and the
mobility depend on the strain rate the latter exhibits a rather weak
dependency. Somewhat surprisingly, we find that the initial decay of response
and correlation functions coincide, allowing for an interpretation in terms of
an 'effective temperature'. Such a phenomenological effective temperature
recovers the Einstein relation in nonequilibrium. We show that our data is well
described by two expansions to lowest order in the strain rate.Comment: submitted to EP
On measuring colloidal volume fractions
Hard-sphere colloids are popular as models for testing fundamental theories
in condensed matter and statistical physics, from crystal nucleation to the
glass transition. A single parameter, the volume fraction (phi), characterizes
an ideal, monodisperse hard-sphere suspension. In comparing experiments with
theories and simulation, researchers to date have paid little attention to
likely uncertainties in experimentally-quoted phi values. We critically review
the experimental measurement of phi in hard-sphere colloids, and show that
while statistical uncertainties in comparing relative values of phi can be as
low as 0.0001, systematic errors of 3-6% are probably unavoidable. The
consequences of this are illustrated by way of a case study comparing
literature data sets on hard-sphere viscosity and diffusion.Comment: 11 page
The Physics of the Colloidal Glass Transition
As one increases the concentration of a colloidal suspension, the system
exhibits a dramatic increase in viscosity. Structurally, the system resembles a
liquid, yet motions within the suspension are slow enough that it can be
considered essentially frozen. This kinetic arrest is the colloidal glass
transition. For several decades, colloids have served as a valuable model
system for understanding the glass transition in molecular systems. The spatial
and temporal scales involved allow these systems to be studied by a wide
variety of experimental techniques. The focus of this review is the current
state of understanding of the colloidal glass transition. A brief introduction
is given to important experimental techniques used to study the glass
transition in colloids. We describe features of colloidal systems near and in
glassy states, including tremendous increases in viscosity and relaxation
times, dynamical heterogeneity, and ageing, among others. We also compare and
contrast the glass transition in colloids to that in molecular liquids. Other
glassy systems are briefly discussed, as well as recently developed synthesis
techniques that will keep these systems rich with interesting physics for years
to come.Comment: 56 pages, 18 figures, Revie
Quantitative imaging of concentrated suspensions under flow
We review recent advances in imaging the flow of concentrated suspensions,
focussing on the use of confocal microscopy to obtain time-resolved information
on the single-particle level in these systems. After motivating the need for
quantitative (confocal) imaging in suspension rheology, we briefly describe the
particles, sample environments, microscopy tools and analysis algorithms needed
to perform this kind of experiments. The second part of the review focusses on
microscopic aspects of the flow of concentrated model hard-sphere-like
suspensions, and the relation to non-linear rheological phenomena such as
yielding, shear localization, wall slip and shear-induced ordering. Both
Brownian and non-Brownian systems will be described. We show how quantitative
imaging can improve our understanding of the connection between microscopic
dynamics and bulk flow.Comment: Review on imaging hard-sphere suspensions, incl summary of
methodology. Submitted for special volume 'High Solid Dispersions' ed. M.
Cloitre, Vol. xx of 'Advances and Polymer Science' (Springer, Berlin, 2009);
22 pages, 16 fig