713 research outputs found
Graphene Multi-Protonation: a Cooperative Mechanism for Proton Permeation
The interaction between protons and graphene is attracting a large interest
due to recent experiments showing that these charged species permeate through
the 2D material following a low barrier (~ 0.8 eV) activated process. A
possible explanation involves the flipping of a chemisorbed proton (rotation of
the C-H bond from one to the other side of the carbon layer) and previous
studies have found so far that the energy barriers (around 3.5 eV) are too high
to explain the experimental findings. Contrarily to the previously adopted
model assuming an isolated proton, in this work we consider protonated graphene
at high local coverage and explore the role played by nearby chemisorbed
protons in the permeation process. By means of density functional theory
calculations exploiting large molecular prototypes for graphene it is found
that, when various protons are adsorbed on the same carbon hexagonal ring, the
permeation barrier can be reduced down to 1.0 eV. The related mechanism is
described in detail and could shed a new light on the interpretation of the
experimental observations for proton permeation through graphene.Comment: 16 pages, 5 figure
Three-Dimensional Wave Packet Approach for the Quantum Transport of Atoms through Nanoporous Membranes
Quantum phenomena are relevant to the transport of light atoms and molecules
through nanoporous two-dimensional (2D) membranes. Indeed, confinement provided
by (sub-)nanometer pores enhances quantum effects such as tunneling and zero
point energy (ZPE), even leading to quantum sieving of different isotopes of a
given element. However, these features are not always taken into account in
approaches where classical theories or approximate quantum models are
preferred. In this work we present an exact three-dimensional wave packet
propagation treatment for simulating the passage of atoms through periodic 2D
membranes. Calculations are reported for the transmission of He and He
through graphdiyne as well as through a holey graphene model. For
He-graphdiyne, estimations based on tunneling-corrected transition state theory
are correct: both tunneling and ZPE effects are very important but competition
between each other leads to a moderately small He/He selectivity. Thus,
formulations that neglect one or another quantum effect are inappropriate. For
the transport of He isotopes through leaky graphene, the computed transmission
probabilities are highly structured suggesting widespread selective adsorption
resonances and the resulting rate coefficients and selectivity ratios are not
in agreement with predictions from transition state theory. Present approach
serves as a benchmark for studies of the range of validity of more approximate
methods.Comment: 4 figure
Graphdiyne based membranes: exceptional performances for helium separation applications
Graphdiyne is a novel two-dimensional material deriving from graphene that
has been recently synthesized and featuring uniformly distributed sub-nanometer
pores. We report accurate calculations showing that graphdiyne pores permit an
almost unimpeded helium transport which can be used for its chemical and
isotopic separation. Exceptionally high He/CH_4 selectivities are found which
largely exceed the performance of the best membranes used to date for
extraction from natural gas. Moreover, by exploiting slight differences in the
tunneling probabilities of ^3He and ^4He, we also find promising results for
the separation of the Fermionic isotope at low temperature
Three-Dimensional Wave-Packet Calculations of the Transmission of He Isotopes through Graphynes Membranes
Mendoza, Argentina. 9th-13st of May 2016 ; http://photodynamics9.wixsite.com/phd9N
Helium Isotopes Quantum Sieving Through Graphtriyne Membranes
We report accurate quantum calculations of the sieving of Helium atoms by
two-dimensional (2D) graphtriyne layers with a new interaction potential.
Thermal rate constants and permeances in an ample temperature range are
computed and compared for both Helium isotopes. With a pore larger than
graphdiyne, the most common member of the gamma - graphyne family, it could be
expected that the appearance of quantum effects were more limited. We find,
however, a strong quantum behavior that can be attributed to the presence of
selective adsorption resonances, with a pronounced effect in the low
temperature regime. This effect leads to the appearance of some selectivity at
very low temperatures and the possibility for the heavier isotope to cross the
membrane more efficiently than the lighter, contrarily to what happened with
graphdiyne membranes, where the sieving at low energy is predominantly ruled by
quantum tunneling. The use of more approximate methods could be not advisable
in these situations and prototypical transition state theory (TST) treatments
might lead to large errors
Transmission of Helium Isotopes through Graphdiyne Pores: Tunneling versus Zero Point Energy Effects
7 pags.; 7 figs.; 1 tab.Recent progress in the production of new two-dimensional (2D) nanoporous materials is attracting considerable interest for applications to isotope separation in gases. In this paper we report a computational study of the transmission of 4 He and 3 He through the (subnanometer) pores of graphdiyne, a recently synthesized 2D carbon material. The He−graphdiyne interaction is represented by a force field parametrized upon ab initio calculations, and the 4 He/3 He selectivity is analyzed by tunneling-corrected transition state theory. We have found that both zero point energy (of the in-pore degrees of freedom) and tunneling effects play an extraordinary role at low temperatures (≈20−30 K). However, both quantum features work in opposite directions in such a way that the selectivity ratio does not reach an acceptable value. Nevertheless, the efficiency of zero point energy is in general larger, so that 4 He tends to diffuse faster than 3
He through the graphdiyne membrane, with a maximum performance at 23 K. Moreover,
it is found that the transmission rates are too small in the studied temperature range, precluding practical applications. It is concluded that the role of the in-pore degrees of freedom should be included in computations of the transmission probabilities of molecules through nanoporous materials. © 2015 American Chemical SocietyThe work has been funded by Spanish MINECO grant
FIS2013-48275-C2-1-P. Allocation of computing time by
CESGA (Spain) and support by the COST-CMTS Action
CM1405 “Molecules in Motion (MOLIM)” are also acknowledged.Peer reviewe
Temperature-independent quantum logic for molecular spectroscopy
We propose a fast and non-destructive spectroscopic method for single
molecular ions that implements quantum logic schemes between an atomic ion and
the molecular ion of interest. Our proposal relies on a hybrid coherent
manipulation of the two-ion system, using optical or magnetic forces depending
on the types of molecular levels to be addressed (Zeeman, rotational,
vibrational or electronic degrees of freedom). The method is especially suited
for the non-destructive precision spectroscopy of single molecular ions, and
sets a starting point for new hybrid quantum computation schemes that combine
molecular and atomic ions, covering the measurement and entangling steps.Comment: v3. Substantially enlarged manuscript with details of derivations and
calculations in two appendices. To appear in PR
Interactions in Oxygen: from the gas to high pressure solid phases
7th International Meeting on Photodynamics, Maresias SP, Brazil, 14-20 Oct. 2012Peer Reviewe
Does like seek like?: the formation of working groups in a programming project
In a course of the degree of computer science, the programming project has changed from individual to teamed work, tentatively in couples (pair programming). Students have full freedom to team up with minimum intervention from teachers. The analysis of the couples made indicates that students do not tend to associate with students with a similar academic performance, maybe because general cognitive parameters do not govern the choice of academic partners. Pair programming seems to give great results, so the efforts of future research in this field should focus precisely on how these pairs are formed, underpinning the mechanisms of human social interactionsPeer Reviewe
The Molecular Oxygen Tetramer: Intermolecular Interactions and Implications for the Solid Phase
Recent data have determined that the structure of the high pressure
phase of solid oxygen consists of clusters composed of four O
molecules. This finding has opened the question about the nature of the
intermolecular interactions within the molecular oxygen tetramer. We use
multiconfigurational ab initio calculations to obtain an adequate
characterization of the ground singlet state of
(O) which is compatible with the non magnetic character of the
phase. In contrast to previous suggestions implying chemical
bonding, we show that (O) is a van der Waals like cluster where
exchange interactions preferentially stabilize the singlet state. However, as
the cluster shrinks, there is an extra stabilization due to many-body
interactions that yields a significant softening of the repulsive wall. We show
that this short range behavior is a key issue for the understanding of the
structure of -oxygen
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