713 research outputs found
Nonstatistical dynamics on potentials exhibiting reaction path bifurcations and valley-ridge inflection points
We study reaction dynamics on a model potential energy surface exhibiting
post-transition state bifurcation in the vicinity of a valley ridge inflection
point. We compute fractional yields of products reached after the VRI region is
traversed, both with and without dissipation. It is found that apparently minor
variations in the potential lead to significant changes in the reaction
dynamics. Moreover, when dissipative effects are incorporated, the product
ratio depends in a complicated and highly non-monotonic fashion on the
dissipation parameter. Dynamics in the vicinity of the VRI point itself play
essentially no role in determining the product ratio, except in the highly
dissipative regime.Comment: 33 pages, 10 figures, corrected the author name in reference [6
Isomerization dynamics of a buckled nanobeam
We analyze the dynamics of a model of a nanobeam under compression. The model
is a two mode truncation of the Euler-Bernoulli beam equation subject to
compressive stress. We consider parameter regimes where the first mode is
unstable and the second mode can be either stable or unstable, and the
remaining modes (neglected) are always stable. Material parameters used
correspond to silicon. The two mode model Hamiltonian is the sum of a
(diagonal) kinetic energy term and a potential energy term. The form of the
potential energy function suggests an analogy with isomerisation reactions in
chemistry. We therefore study the dynamics of the buckled beam using the
conceptual framework established for the theory of isomerisation reactions.
When the second mode is stable the potential energy surface has an index one
saddle and when the second mode is unstable the potential energy surface has an
index two saddle and two index one saddles. Symmetry of the system allows us to
construct a phase space dividing surface between the two "isomers" (buckled
states). The energy range is sufficiently wide that we can treat the effects of
the index one and index two saddles in a unified fashion. We have computed
reactive fluxes, mean gap times and reactant phase space volumes for three
stress values at several different energies. In all cases the phase space
volume swept out by isomerizing trajectories is considerably less than the
reactant density of states, proving that the dynamics is highly nonergodic. The
associated gap time distributions consist of one or more `pulses' of
trajectories. Computation of the reactive flux correlation function shows no
sign of a plateau region; rather, the flux exhibits oscillatory decay,
indicating that, for the 2-mode model in the physical regime considered, a rate
constant for isomerization does not exist.Comment: 42 pages, 6 figure
Distribution and Excretion of TEGDMA in Guinea Pigs and Mice
The monomer triethyleneglycoldimethacrylate (TEGDMA) is used as a diluent in many resin-based dental materials. It was previously shown in vitro that TEGDMA was released into the adjacent biophase from such materials during the first days after placement. In this study, the uptake, distribution, and excretion of 14C-TEGDMA applied via gastric, intradermal, and intravenous administration at dose levels well above those encountered in dental care were examined in vivo in guinea pigs and mice as a test of the hypothesis that TEGDMA reaches cytotoxic levels in mammalian tissues. 14C-TEGDMA was taken up rapidly from the stomach and small intestine after gastric administration in both species and was widely distributed in the body following administration by each route. Most 14C was excreted within one day as 14 CO2. The peak equivalent TEGDMA levels in all mouse and guinea pig tissues examined were at least 1000-fold less than known toxic levels. The study therefore did not support the hypothesis
Bottlenecks to vibrational energy flow in OCS: Structures and mechanisms
Finding the causes for the nonstatistical vibrational energy relaxation in
the planar carbonyl sulfide (OCS) molecule is a longstanding problem in
chemical physics: Not only is the relaxation incomplete long past the predicted
statistical relaxation time, but it also consists of a sequence of abrupt
transitions between long-lived regions of localized energy modes. We report on
the phase space bottlenecks responsible for this slow and uneven vibrational
energy flow in this Hamiltonian system with three degrees of freedom. They
belong to a particular class of two-dimensional invariant tori which are
organized around elliptic periodic orbits. We relate the trapping and
transition mechanisms with the linear stability of these structures.Comment: 13 pages, 13 figure
Attosecond electron thermalization by laser-driven electron recollision in atoms
Nonsequential multiple ionization of atoms in intense laser fields is
initiated by a recollision between an electron, freed by tunneling, and its
parent ion. Following recollision, the initial electron shares its energy with
several bound electrons. We use a classical model based on rapid electron
thermalization to interpret recent experiments. For neon, good agreement with
the available data is obtained with an upper bound of 460 attoseconds for the
thermalization time.Comment: 5 pages revtex and 4 figures (eps files
Gaussian excitations model for glass-former dynamics and thermodynamics
We describe a model for the thermodynamics and dynamics of glass-forming
liquids in terms of excitations from an ideal glass state to a Gaussian
manifold of configurationally excited states. The quantitative fit of this
three parameter model to the experimental data on excess entropy and heat
capacity shows that ``fragile'' behavior, indicated by a sharply rising excess
heat capacity as the glass transition is approached from above, occurs in
anticipation of a first-order transition -- usually hidden below the glass
transition -- to a ``strong'' liquid state of low excess entropy. The dynamic
model relates relaxation to a hierarchical sequence of excitation events each
involving the probability of accumulating sufficient kinetic energy on a
separate excitable unit. Super-Arrhenius behavior of the relaxation rates, and
the known correlation of kinetic with thermodynamic fragility, both follow from
the way the rugged landscape induces fluctuations in the partitioning of energy
between vibrational and configurational manifolds. A relation is derived in
which the configurational heat capacity, rather than the configurational
entropy of the Adam Gibbs equation, controls the temperature dependence of the
relaxation times, and this gives a comparable account of the experimental
observations.Comment: 21 pp., 17 fig
Adaptive walks on time-dependent fitness landscapes
The idea of adaptive walks on fitness landscapes as a means of studying
evolutionary processes on large time scales is extended to fitness landscapes
that are slowly changing over time. The influence of ruggedness and of the
amount of static fitness contributions are investigated for model landscapes
derived from Kauffman's landscapes. Depending on the amount of static
fitness contributions in the landscape, the evolutionary dynamics can be
divided into a percolating and a non-percolating phase. In the percolating
phase, the walker performs a random walk over the regions of the landscape with
high fitness.Comment: 7 pages, 6 eps-figures, RevTeX, submitted to Phys. Rev.
Electron attachment to SF6 and lifetimes of SF6- negative ions
We study the process of low-energy electron capture by the SF6 molecule. Our
approach is based on the model of Gauyacq and Herzenberg [J. Phys. B 17, 1155
(1984)] in which the electron motion is coupled to the fully symmetric
vibrational mode through a weakly bound or virtual s state. By tuning the two
free parameters of the model, we achieve an accurate description of the
measured electron attachment cross section and good agreement with vibrational
excitation cross sections of the fully symmetric mode. An extension of the
model provides a limit on the characteristic time of intramolecular vibrational
relaxation in highly-excited SF6-. By evaluating the total vibrational spectrum
density of SF6-, we estimate the widths of the vibrational Feshbach resonances
of the long-lived negative ion. We also analyse the possible distribution of
the widths and its effect on the lifetime measurements, and investigate
nonexponential decay features in metastable SF6-.Comment: 22 pages, 10 figures, submitted to Phys. Rev.
On Justification, Idealization, and Discursive Purchase
Conceptions of acceptability-based moral or political justification take it that authoritative acceptability, widely conceived, constitutes, or contributes to, validity, or justification. There is no agreement as to what bar for authoritativeness such justification may employ. The paper engages the issue in relation to (i) the level of idealization that a bar for authoritativeness, ψ, imparts to a standard of acceptability-based justification, S, and (ii) the degree of discursive purchase of the discursive standing that S accords to people when it builds ψ. I argue that (i) and (ii) are interdependent: high idealization values entail low discursive purchase, while high degrees of purchase require low idealization values. I then distinguish between alethic conceptions of justification that prioritize ends that commit to high idealization values, and recognitive conceptions that favor high discursive purchase. On this basis, I argue for a moderately recognitivist constraint on idealization. To render the recognitive discursive minimum available to relevant people at the site of justification, S should set ψ low enough so that it is a genuine option for actual people to reject relevant views in ways that S recognizes as authoritative. (The Appendix applies this to a Forst-type view of reciprocity of reasons to draw out some limitations of this view.) [Draft available from author on request.
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