809 research outputs found
Charging induced asymmetry in molecular conductors
We investigate the origin of asymmetry in various measured current-voltage
(I-V) characteristics of molecules with no inherent spatial asymmetry, with
particular focus on a recent break junction measurement. We argue that such
asymmetry arises due to unequal coupling with the contacts and a consequent
difference in charging effects, which can only be captured in a self-consistent
model for molecular conduction. The direction of the asymmetry depends on the
sign of the majority carriers in the molecule. For conduction through highest
occupied molecular orbitals (i.e. HOMO or p-type conduction), the current is
smaller for positive voltage on the stronger contact, while for conduction
through lowest unoccupied molecular orbitals (i.e. LUMO or n-type conduction),
the sense of the asymmetry is reversed. Within an extended Huckel description
of the molecular chemistry and the contact microstructure (with two adjustable
parameters, the position of the Fermi energy and the sulphur-gold bond length),
an appropriate description of Poisson's equation, and a self-consistently
coupled non-equilibrium Green's function (NEGF) description of transport, we
achieve good agreement between theoretical and experimental I-V
characteristics, both in shape as well as overall magnitude.Comment: length of the paper has been extended (4 pages to 6 pages), two new
figures have been added (3 figures to 5 figures), has been accepted for PR
Efficiency Improvements for Encrypt-to-Self
Recent work by Pijnenburg and Poettering (ESORICS'20) explores the novel
cryptographic Encrypt-to-Self primitive that is dedicated to use cases of
symmetric encryption where encryptor and decryptor coincide. The primitive is
envisioned to be useful whenever a memory-bounded computing device is required
to encrypt some data with the aim of temporarily depositing it on an untrusted
storage device. While the new primitive protects the confidentiality of
payloads as much as classic authenticated encryption primitives would do, it
provides considerably better authenticity guarantees: Specifically, while
classic solutions would completely fail in a context involving user
corruptions, if an encrypt-to-self scheme is used to protect the data, all
ciphertexts and messages fully remain unforgeable.
To instantiate their encrypt-to-self primitive, Pijnenburg et al propose a
mode of operation of the compression function of a hash function, with a
carefully designed encoding function playing the central role in the
serialization of the processed message and associated data. In the present work
we revisit the design of this encoding function. Without questioning its
adequacy for securely accomplishing the encrypt-to-self job, we improve on it
from a technical/implementational perspective by proposing modifications that
alleviate certain conditions that would inevitably require implementations to
disrespect memory alignment restrictions imposed by the word-wise operation of
modern CPUs, ultimately leading to performance penalties. Our main
contributions are thus to propose an improved encoding function, to explain why
it offers better performance, and to prove that it provides as much security as
its predecessor. We finally report on our open-source implementation of the
encrypt-to-self primitive based on the new encoding function.Comment: this is the full version of content that appears at CYSARM'2
Driving current through single organic molecules
We investigate electronic transport through two types of conjugated
molecules. Mechanically controlled break-junctions are used to couple thiol
endgroups of single molecules to two gold electrodes. Current-voltage
characteristics (IVs) of the metal-molecule-metal system are observed. These
IVs reproduce the spatial symmetry of the molecules with respect to the
direction of current flow. We hereby unambigously detect an intrinsic property
of the molecule, and are able to distinguish the influence of both the molecule
and the contact to the metal electrodes on the transport properties of the
compound system.Comment: 4 pages, 5 figure
Orbital Interaction Mechanisms of Conductance Enhancement and Rectification by Dithiocarboxylate Anchoring Group
We study computationally the electron transport properties of
dithiocarboxylate terminated molecular junctions. Transport properties are
computed self-consistently within density functional theory and nonequilibrium
Green's functions formalism. A microscopic origin of the experimentally
observed current amplification by dithiocarboxylate anchoring groups is
established. For the 4,4'-biphenyl bis(dithiocarboxylate) junction, we find
that the interaction of the lowest unoccupied molecular orbital (LUMO) of the
dithiocarboxylate anchoring group with LUMO and highest occupied molecular
orbital (HOMO) of the biphenyl part results in bonding and antibonding
resonances in the transmission spectrum in the vicinity of the electrode Fermi
energy. A new microscopic mechanism of rectification is predicted based on the
electronic structure of asymmetrical anchoring groups. We show that the peaks
in the transmission spectra of 4'-thiolato-biphenyl-4-dithiocarboxylate
junction respond differently to the applied voltage. Depending upon the origin
of a transmission resonance in the orbital interaction picture, its energy can
be shifted along with the chemical potential of the electrode to which the
molecule is more strongly or more weakly coupled
Current rectification by simple molecular quantum dots: an ab-initio study
We calculate a current rectification by molecules containing a conjugated
molecular group sandwiched between two saturated (insulating) molecular groups
of different length (molecular quantum dot) using an ab-initio non-equilibrium
Green's function method. In particular, we study S-(CH2)m-C10H6-(CH2)n-S
dithiol with Naphthalene as a conjugated central group. The rectification
current ratio ~35 has been observed at m = 2 and n = 10, due to resonant
tunneling through the molecular orbital (MO) closest to the electrode Fermi
level (lowest unoccupied MO in the present case). The rectification is limited
by interference of other conducting orbitals, but can be improved by e.g.
adding an electron withdrawing group to the naphthalene.Comment: 8 pages, 9 figure
Molecular Wires Acting as Coherent Quantum Ratchets
The effect of laser fields on the electron transport through a molecular wire
being weakly coupled to two leads is investigated. The molecular wire acts as a
coherent quantum ratchet if the molecule is composed of periodically arranged,
asymmetric chemical groups. This setup presents a quantum rectifier with a
finite dc-response in the absence of a static bias. The nonlinear current is
evaluated in closed form within the Floquet basis of the isolated, driven wire.
The current response reveals multiple current reversals together with a
nonlinear dependence (reflecting avoided quasi-energy crossings) on both, the
amplitude and the frequency of the laser field. The current saturates for long
wires at a nonzero value, while it may change sign upon decreasing its length.Comment: 4 pages, 4 figures, RevTeX
Bi-stable tunneling current through a molecular quantum dot
An exact solution is presented for tunneling through a negative-U d-fold
degenerate molecular quantum dot weakly coupled to electrical leads. The tunnel
current exhibits hysteresis if the level degeneracy of the negative-U dot is
larger than two (d>2). Switching occurs in the voltage range V1 < V < V2 as a
result of attractive electron correlations in the molecule, which open up a new
conducting channel when the voltage is above the threshold bias voltage V2.
Once this current has been established, the extra channel remains open as the
voltage is reduced down to the lower threshold voltage V1. Possible
realizations of the bi-stable molecular quantum dots are fullerenes, especially
C60, and mixed-valence compounds.Comment: 5 pages, 1 figure. (v2) Figure updated to compare the current
hysteresis for degeneracies d=4 and d>>1 of the level in the dot, minor
corrections in the text. To appear in Phys. Rev.
The SND proteins constitute an alternative targeting route to the endoplasmic reticulum.
In eukaryotes, up to one-third of cellular proteins are targeted to the endoplasmic reticulum, where they undergo folding, processing, sorting and trafficking to subsequent endomembrane compartments(1). Targeting to the endoplasmic reticulum has been shown to occur co-translationally by the signal recognition particle (SRP) pathway(2) or post-translationally by the mammalian transmembrane recognition complex of 40 kDa (TRC40)(3,4) and homologous yeast guided entry of tail-anchored proteins (GET)(5,6) pathways. Despite the range of proteins that can be catered for by these two pathways, many proteins are still known to be independent of both SRP and GET, so there seems to be a critical need for an additional dedicated pathway for endoplasmic reticulum relay(7,8). We set out to uncover additional targeting proteins using unbiased high-content screening approaches. To this end, we performed a systematic visual screen using the yeast Saccharomyces cerevisiae(9,10), and uncovered three uncharacterized proteins whose loss affected targeting. We suggest that these proteins work together and demonstrate that they function in parallel with SRP and GET to target a broad range of substrates to the endoplasmic reticulum. The three proteins, which we name Snd1, Snd2 and Snd3 (for SRP-independent targeting), can synthetically compensate for the loss of both the SRP and GET pathways, and act as a backup targeting system. This explains why it has previously been difficult to demonstrate complete loss of targeting for some substrates. Our discovery thus puts in place an essential piece of the endoplasmic reticulum targeting puzzle, highlighting how the targeting apparatus of the eukaryotic cell is robust, interlinked and flexible
Kirchhoff's Rule for Quantum Wires
In this article we formulate and discuss one particle quantum scattering
theory on an arbitrary finite graph with open ends and where we define the
Hamiltonian to be (minus) the Laplace operator with general boundary conditions
at the vertices. This results in a scattering theory with channels. The
corresponding on-shell S-matrix formed by the reflection and transmission
amplitudes for incoming plane waves of energy is explicitly given in
terms of the boundary conditions and the lengths of the internal lines. It is
shown to be unitary, which may be viewed as the quantum version of Kirchhoff's
law. We exhibit covariance and symmetry properties. It is symmetric if the
boundary conditions are real. Also there is a duality transformation on the set
of boundary conditions and the lengths of the internal lines such that the low
energy behaviour of one theory gives the high energy behaviour of the
transformed theory. Finally we provide a composition rule by which the on-shell
S-matrix of a graph is factorizable in terms of the S-matrices of its
subgraphs. All proofs only use known facts from the theory of self-adjoint
extensions, standard linear algebra, complex function theory and elementary
arguments from the theory of Hermitean symplectic forms.Comment: 40 page
Electron transport through dipyrimidinyl-diphenyl diblock molecular wire: protonation effect
Recently, rectifying direction inversion has been observed in
dipyrimidinyl-diphenyl (PMPH) diblock molecular wire [J. Am. Chem. Soc. (2005)
127, 10456], and a protonation mechanism was suggested to explain this
interesting phenomena. In this paper, we study the protonation effect on
transport properties of PMPH molecule by first principles calculations. No
significant rectification is found for the pristine diblock molecular wire.
Protonation leads to conductance enhancement and rectification. However, for
all considered junctions with rectifying effect, the preferential current
directions are samely from dipyrimidinyl side to diphenyl side. Effect of
molecule-electrode anchoring geometry is studied, and it is not responsible for
the discrepancy between experiment and theory.Comment: 17 pages, 8 figure
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