814 research outputs found
Enhanced dispersion interaction between quasi-one dimensional conducting collinear structures
Recent investigations have highlighted the failure of a sum of terms
to represent the dispersion interaction in parallel metallic, anisotropic,
linear or planar nanostructures [J. F. Dobson, A. White, and A. Rubio, Phys.
Rev. Lett. 96, 073201 (2006) and references therein]. By applying a simple
coupled plasmon approach and using electron hydrodynamics, we numerically
evaluate the dispersion (non-contact van der Waals) interaction between two
conducting wires in a collinear pointing configuration. This case is compared
to that of two insulating wires in an identical geometry, where the dispersion
interaction is modelled both within a pairwise summation framework, and by
adding a pinning potential to our theory leading to a standard oscillator-type
model of insulating dielectric behavior. Our results provide a further example
of enhanced dispersion interaction between two conducting nanosystems compared
to the case of two insulating ones. Unlike our previous work, this calculation
explores a region of relatively close coupling where, although the electronic
clouds do not overlap, we are still far from the asymptotic region where a
single power law describes the dispersion energy. We find that strong
differences in dispersion attraction between metallic and semiconducting /
insulating cases persist into this non-asymptotic region. While our theory will
need to be supplemented with additional short-ranged terms when the electronic
clouds overlap, it does not suffer from the short-distance divergence exhibited
by purely asymptotic theories, and gives a natural saturation of the dispersion
energy as the wires come into contact.Comment: 10 pages, 5 figures. Added new extended numerical calculations, new
figures, extra references and heavily revised tex
Atomic Supersymmetry, Rydberg Wave Packets, and Radial Squeezed States
We study radial wave packets produced by short-pulsed laser fields acting on
Rydberg atoms, using analytical tools from supersymmetry-based quantum-defect
theory. We begin with a time-dependent perturbative calculation for
alkali-metal atoms, incorporating the atomic-excitation process. This provides
insight into the general wave packet behavior and demonstrates agreement with
conventional theory. We then obtain an alternative analytical description of a
radial wave packet as a member of a particular family of squeezed states, which
we call radial squeezed states. By construction, these have close to minimum
uncertainty in the radial coordinates during the first pass through the outer
apsidal point. The properties of radial squeezed states are investigated, and
they are shown to provide a description of certain aspects of Rydberg atoms
excited by short-pulsed laser fields. We derive expressions for the time
evolution and the autocorrelation of the radial squeezed states, and we study
numerically and analytically their behavior in several alkali-metal atoms. Full
and fractional revivals are observed. Comparisons show agreement with other
theoretical results and with experiment.Comment: published in Physical Review
Quantum mechanics/molecular mechanics modeling of drug metabolism:Mexiletine N-hydroxylation by cytochrome P450 1A2
The mechanism of cytochrome P450(CYP)-catalyzed
hydroxylation of
primary amines is currently unclear and is relevant to drug metabolism;
previous small model calculations have suggested two possible mechanisms:
direct N-oxidation and H-abstraction/rebound. We have modeled the
N-hydroxylation of (<i>R</i>)-mexiletine in CYP1A2 with
hybrid quantum mechanics/molecular mechanics (QM/MM) methods, providing
a more detailed and realistic model. Multiple reaction barriers have
been calculated at the QM(B3LYP-D)/MM(CHARMM27) level for the direct
N-oxidation and H-abstraction/rebound mechanisms. Our calculated barriers
indicate that the direct N-oxidation mechanism is preferred and proceeds
via the doublet spin state of Compound I. Molecular dynamics simulations
indicate that the presence of an ordered water molecule in the active
site assists in the binding of mexiletine in the active site, but
this is not a prerequisite for reaction via either mechanism. Several
active site residues play a role in the binding of mexiletine in the
active site, including Thr124 and Phe226. This work reveals key details
of the N-hydroxylation of mexiletine and further demonstrates that
mechanistic studies using QM/MM methods are useful for understanding
drug metabolism
Semiconducting Monolayer Materials as a Tunable Platform for Excitonic Solar Cells
The recent advent of two-dimensional monolayer materials with tunable
optoelectronic properties and high carrier mobility offers renewed
opportunities for efficient, ultra-thin excitonic solar cells alternative to
those based on conjugated polymer and small molecule donors. Using
first-principles density functional theory and many-body calculations, we
demonstrate that monolayers of hexagonal BN and graphene (CBN) combined with
commonly used acceptors such as PCBM fullerene or semiconducting carbon
nanotubes can provide excitonic solar cells with tunable absorber gap,
donor-acceptor interface band alignment, and power conversion efficiency, as
well as novel device architectures. For the case of CBN-PCBM devices, we
predict the limit of power conversion efficiencies to be in the 10 - 20% range
depending on the CBN monolayer structure. Our results demonstrate the
possibility of using monolayer materials in tunable, efficient, polymer-free
thin-film solar cells in which unexplored exciton and carrier transport regimes
are at play.Comment: 7 pages, 5 figure
Desorption of n-alkanes from graphene: a van der Waals density functional study
A recent study of temperature programmed desorption (TPD) measurements of
small n-alkanes (CNH2N+2) from C(0001) deposited on Pt(111) shows a linear
relationship of the desorption energy with increasing n-alkane chain length. We
here present a van der Waals density functional study of the desorption barrier
energy of the ten smallest n-alkanes (N = 1 to 10) from graphene. We find
linear scaling with N, including a nonzero intercept with the energy axis,
i.e., an offset at the extrapolation to N = 0. This calculated offset is
quantitatively similar to the results of the TPD measurements. From further
calculations of the polyethylene polymer we offer a suggestion for the origin
of the offset.Comment: 3 pictures, 1 tabl
Graphite and Hexagonal Boron-Nitride Possess the Same Interlayer Distance. Why?
Graphite and hexagonal boron nitride (h-BN) are two prominent members of the
family of layered materials possessing a hexagonal lattice. While graphite has
non-polar homo-nuclear C-C intra-layer bonds, h-BN presents highly polar B-N
bonds resulting in different optimal stacking modes of the two materials in
bulk form. Furthermore, the static polarizabilities of the constituent atoms
considerably differ from each other suggesting large differences in the
dispersive component of the interlayer bonding. Despite these major differences
both materials present practically identical interlayer distances. To
understand this finding, a comparative study of the nature of the interlayer
bonding in both materials is presented. A full lattice sum of the interactions
between the partially charged atomic centers in h-BN results in vanishingly
small monopolar electrostatic contributions to the interlayer binding energy.
Higher order electrostatic multipoles, exchange, and short-range correlation
contributions are found to be very similar in both materials and to almost
completely cancel out by the Pauli repulsions at physically relevant interlayer
distances resulting in a marginal effective contribution to the interlayer
binding. Further analysis of the dispersive energy term reveals that despite
the large differences in the individual atomic polarizabilities the
hetero-atomic B-N C6 coefficient is very similar to the homo-atomic C-C
coefficient in the hexagonal bulk form resulting in very similar dispersive
contribution to the interlayer binding. The overall binding energy curves of
both materials are thus very similar predicting practically the same interlayer
distance and very similar binding energies.Comment: 18 pages, 5 figures, 2 table
The interlayer cohesive energy of graphite from thermal desorption of polyaromatic hydrocarbons
We have studied the interaction of polyaromatic hydrocarbons (PAHs) with the
basal plane of graphite using thermal desorption spectroscopy. Desorption
kinetics of benzene, naphthalene, coronene and ovalene at sub-monolayer
coverages yield activation energies of 0.50 eV, 0.85 eV, 1.40 eV and 2.1 eV,
respectively. Benzene and naphthalene follow simple first order desorption
kinetics while coronene and ovalene exhibit fractional order kinetics owing to
the stability of 2-D adsorbate islands up to the desorption temperature.
Pre-exponential frequency factors are found to be in the range
- as obtained from both Falconer--Madix (isothermal
desorption) analysis and Antoine's fit to vapour pressure data. The resulting
binding energy per carbon atom of the PAH is 5 meV and can be identified
with the interlayer cohesive energy of graphite. The resulting cleavage energy
of graphite is ~meV/atom which is considerably larger than previously
reported experimental values.Comment: 8 pages, 4 figures, 2 table
Unified Treatment of Asymptotic van der Waals Forces
In a framework for long-range density-functional theory we present a unified
full-field treatment of the asymptotic van der Waals interaction for atoms,
molecules, surfaces, and other objects. The only input needed consists of the
electron densities of the interacting fragments and the static polarizability
or the static image plane, which can be easily evaluated in a ground-state
density-functional calculation for each fragment. Results for separated atoms,
molecules, and for atoms/molecules outside surfaces are in agreement with those
of other, more elaborate, calculations.Comment: 6 pages, 5 figure
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