5,164 research outputs found
Isotopic replacement in ionic systems: the 4He2+ + 3He -> 3He4He+ + 4He reaction
Full quantum dynamics calculations have been carried out for the ionic
reaction 4He2+ + 3He and state-to-state reactive probabilities have been
obtained using both a time-dependent (TD) and a time-independent (TI) approach.
An accurate ab-initio potential energy surface has been employed for the
present quantum dynamics and the two sets of results are shown to be in
agreement with each other. The results for zero total angular momentum suggest
a marked presence of atom exchange (isotopic replacement) reaction with
probabilities as high as 60%. The reaction probabilities are only weakly
dependent on the initial vibrational state of the reactants while they are
slightly more sensitive to the degree of rotational excitation. A brief
discussion of the results for selected higher total angular momentum values is
also presented, while the l-shifting approximation [1] has been used to provide
estimates of the total reaction rates for the title process. Such rates are
found to be large enough to possibly become experimentally accessible
Viscoplasticity and large-scale chain relaxation in glassy-polymeric strain hardening
A simple theory for glassy polymeric mechanical response which accounts for
large scale chain relaxation is presented. It captures the crossover from
perfect-plastic response to strong strain hardening as the degree of
polymerization increases, without invoking entanglements. By relating
hardening to interactions on the scale of monomers and chain segments, we
correctly predict its magnitude. Strain activated relaxation arising from the
need to maintain constant chain contour length reduces the dependence of
the characteristic relaxation time by a factor during
active deformation at strain rate . This prediction is consistent
with results from recent experiments and simulations, and we suggest how it may
be further tested experimentally.Comment: The theoretical treatment of the mechanical response has been
significantly revised, and the arguments for coherent relaxation during
active deformation made more transparen
Fabrication of optically smooth Sn thin films
The fabrication of optically smooth thin Sn films by vacuum or
electrodeposition techniques is usually challenging. Little has been published
on how to address this challenge mainly because very few applications require
such smooth Sn surfaces. The excitation of surface plasmon polaritons on Sn
surfaces by prism-based methods represents a case that requires very smooth
surfaces and has motivated this work. It is shown that the deposition rate and
the substrate temperature of a vacuum evaporation method can be optimized to
obtain very smooth Sn films and this is supported by direct imaging evidence
from atomic force microscopy and scanning electron microscopy.Comment: 7 figure
The [4+2]âCycloaddition of αâNitrosoalkenes with Thiochalcones as a Prototype of Periselective HeteroâDielsâAlder ReactionsâExperimental and Computational Studies
The [4+2]âcycloadditions of αânitrosoalkenes with thiochalcones occur with high selectivity at the thioketone moiety of the dienophile providing styrylâsubstituted 4Hâ1,5,2âoxathiazines in moderate to good yields. Of the eight conceivable heteroâDielsâAlder adducts only this isomer was observed, thus a prototype of a highly periselective and regioselective cycloaddition has been identified. Analysis of crude product mixtures revealed that the αânitrosoalkene also adds competitively to the thioketone moiety of the thiochalcone dimer affording bisâheterocyclic [4+2]âcycloadducts. The experiments are supported by highâlevel DFT calculations that were also extended to related heteroâDielsâAlder reactions of other nitroso compounds and thioketones. These calculations reveal that the title cycloadditions are kinetically controlled processes confirming the role of thioketones as superdienophiles. The computational study was also applied to the experimentally studied thiochalcone dimerization, and showed that the 1,2âdithiin and 2Hâthiopyran isomers are in equilibrium with the monomer. Again, the DFT calculations indicate kinetic control of this process
Reconciling Semiclassical and Bohmian Mechanics: III. Scattering states for continuous potentials
In a previous paper [J. Chem. Phys. 121 4501 (2004)] a unique bipolar
decomposition, Psi = Psi1 + Psi2 was presented for stationary bound states Psi
of the one-dimensional Schroedinger equation, such that the components Psi1 and
Psi2 approach their semiclassical WKB analogs in the large action limit. The
corresponding bipolar quantum trajectories, as defined in the usual Bohmian
mechanical formulation, are classical-like and well-behaved, even when Psi has
many nodes, or is wildly oscillatory. A modification for discontinuous
potential stationary stattering states was presented in a second paper [J.
Chem. Phys. 124 034115 (2006)], whose generalization for continuous potentials
is given here. The result is an exact quantum scattering methodology using
classical trajectories. For additional convenience in handling the tunneling
case, a constant velocity trajectory version is also developed.Comment: 16 pages and 14 figure
Elasticity Theory Connection Rules for Epitaxial Interfaces
Elasticity theory provides an accurate description of the long-wavelength
vibrational dynamics of homogeneous crystalline solids, and with supplemental
boundary conditions on the displacement field can also be applied to abrupt
heterojunctions and interfaces. The conventional interface boundary conditions,
or connection rules, require that the displacement field and its associated
stress field be continuous through the interface. We argue, however, that these
boundary conditions are generally incorrect for epitaxial interfaces, and we
give the general procedure for deriving the correct conditions, which depend
essentially on the detailed microscopic structure of the interface. As a simple
application of our theory we analyze in detail a one-dimensional model of an
inhomogeneous crystal, a chain of harmonic oscillators with an abrupt change in
mass and spring stiffness parameters. Our results have implications for phonon
dynamics in nanostructures such as superlattices and nanoparticles, as well as
for the thermal boundary resistance at epitaxial interfaces.Comment: 7 pages, Revte
Dissociative electron attachment to the H2O molecule. II. Nuclear dynamics on coupled electronic surfaces within the local complex potential model
We report the results of a first-principles study of dissociative electron
attachment to H2O. The cross sections are obtained from nuclear dynamics
calculations carried out in full dimensionality within the local complex
potential model by using the multi-configuration time-dependent Hartree method.
The calculations employ our previously obtained global, complex-valued,
potential-energy surfaces for the three (doublet B1, doublet A1, and doublet
B2) electronic Feshbach resonances involved in this process. These three
metastable states of H2O- undergo several degeneracies, and we incorporate both
the Renner-Teller coupling between the B1 and A1 states as well as the conical
intersection between the A1 and B2 states into our treatment. The nuclear
dynamics are inherently multidimensional and involve branching between
different final product arrangements as well as extensive excitation of the
diatomic fragment. Our results successfully mirror the qualitative features of
the major fragment channels observed, but are less successful in reproducing
the available results for some of the minor channels. We comment on the
applicability of the local complex potential model to such a complicated
resonant system.Comment: Corrected version of Phys Rev A 75, 012711 (2007
Effective Temperatures of a Driven System Near Jamming
Fluctuations in a model of a sheared, zero-temperature foam are studied
numerically. Five different quantities that reduce to the true temperature in
an equilibrium thermal system are calculated. All five have the same shear-rate
dependence, and three have the same value. Near the onset of jamming, the
relaxation time is the same function of these three temperatures in the sheared
system as of the true temperature in an unsheared system. These results imply
that statistical mechanics is useful for the system and provide strong support
for the concept of jamming.Comment: 4 pages, 4 postscript figure
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