282 research outputs found
Lattice Dynamics of Solid Cubane within the Quasi-Harmonic Approximation
Solid cubane, which is composed of weakly interacting cubic molecules,
exhibits many unusual and interesting properties, such as a very large thermal
expansion and a first-order phase transition at T=394 K from an
orientationally-ordered phase of R symmetry to a {\it non-cubic}
disordered phase of the same symmetry with a volume expansion of 5.4%, among
the largest ever observed. We study the lattice dynamics of solid cubane within
the quasi-harmonic and rigid-molecule approximation to explain some of these
unusual dynamical properties. The calculated phonon density of states,
dispersion curves and thermal expansion agree surprisingly well with available
experimental data. We find that the amplitude of thermally excited
orientational excitations (i.e. librons) increases rapidly with increasing
temperature and reaches about 35 just before the orientational phase
transition. Hence, the transition is driven by large-amplitude collective
motions of the cubane molecules. Similarly the amplitude of the translational
excitations shows a strong temperature dependence and reaches one tenth of the
lattice constant at T=440 K. This temperature is in fair agreement with the
experimental melting temperature of 405 K, indicating that the Lindemann
criterion works well even for this unusual molecular solid.Comment: 15 pages, 6 figures (devoted to Prof. Ciraci in honor of his sixtieth
birthday
From dimers to the solid-state: Distributed intermolecular force-fields for pyridine
A.A. thanks A.W.E. financial support through the EngDoc studentship from M3S Centre for Doctoral Training (EPSRC Grant No. EP/G036675/1). General computational infrastructure used is developed under No. EPSRC EP/K039229/1
Quantum mechanical calculation of the effects of stiff and rigid constraints in the conformational equilibrium of the Alanine dipeptide
If constraints are imposed on a macromolecule, two inequivalent classical
models may be used: the stiff and the rigid one. This work studies the effects
of such constraints on the Conformational Equilibrium Distribution (CED) of the
model dipeptide HCO-L-Ala-NH2 without any simplifying assumption. We use ab
initio Quantum Mechanics calculations including electron correlation at the MP2
level to describe the system, and we measure the conformational dependence of
all the correcting terms to the naive CED based in the Potential Energy Surface
(PES) that appear when the constraints are considered. These terms are related
to mass-metric tensors determinants and also occur in the Fixman's compensating
potential. We show that some of the corrections are non-negligible if one is
interested in the whole Ramachandran space. On the other hand, if only the
energetically lower region, containing the principal secondary structure
elements, is assumed to be relevant, then, all correcting terms may be
neglected up to peptides of considerable length. This is the first time, as far
as we know, that the analysis of the conformational dependence of these
correcting terms is performed in a relevant biomolecule with a realistic
potential energy function.Comment: 37 pages, 4 figures, LaTeX, BibTeX, AMSTe
Quasi Harmonic Lattice Dynamics and Molecular Dynamics calculations for the Lennard-Jones solids
We present Molecular Dynamics (MD), Quasi Harmonic Lattice Dynamics (QHLD)
and Energy Minimization (EM) calculations for the crystal structure of Ne, Ar,
Kr and Xe as a function of pressure and temperature. New Lennard-Jones (LJ)
parameters are obtained for Ne, Kr and Xe to reproduce the experimental
pressure dependence of the density. We employ a simple method which combines
results of QHLD and MD calculations to achieve densities in good agreement with
experiment from 0 K to melting. Melting is discussed in connection with
intrinsic instability of the solid as given by the QHLD approximation. (See
http://www.fci.unibo.it/~valle for related papers)Comment: 7 pages, 5 figures, REVte
To wet or not to wet: that is the question
Wetting transitions have been predicted and observed to occur for various
combinations of fluids and surfaces. This paper describes the origin of such
transitions, for liquid films on solid surfaces, in terms of the gas-surface
interaction potentials V(r), which depend on the specific adsorption system.
The transitions of light inert gases and H2 molecules on alkali metal surfaces
have been explored extensively and are relatively well understood in terms of
the least attractive adsorption interactions in nature. Much less thoroughly
investigated are wetting transitions of Hg, water, heavy inert gases and other
molecular films. The basic idea is that nonwetting occurs, for energetic
reasons, if the adsorption potential's well-depth D is smaller than, or
comparable to, the well-depth of the adsorbate-adsorbate mutual interaction. At
the wetting temperature, Tw, the transition to wetting occurs, for entropic
reasons, when the liquid's surface tension is sufficiently small that the free
energy cost in forming a thick film is sufficiently compensated by the fluid-
surface interaction energy. Guidelines useful for exploring wetting transitions
of other systems are analyzed, in terms of generic criteria involving the
"simple model", which yields results in terms of gas-surface interaction
parameters and thermodynamic properties of the bulk adsorbate.Comment: Article accepted for publication in J. Low Temp. Phy
Formation and removal of alkylthiolate self-assembled monolayers on gold in aqueous solutions
When a proton attacks cellobiose in the gas phase: ab initio molecular dynamics simulations
Investigations of reaction pathways between a proton and cellobiose (CB), a glucose disaccharide of importance, were carried out in cis and trans CB using Ab Initio Molecular Dynamics (AIMD) simulations starting from optimized configurations where the proton is initially placed near groups with affinity for it. Near and above 300 K, protonated CB (H(+)CB) undergoes several transient reactions including charge transfer to the sugar backbone, water formation and dehydration, ring breaking and glycosidic bond breaking events as well as mutarotation and ring puckering events, all on a 10 ps timescale. cis H(+)CB is energetically favoured over trans H(+)CB in vacuo, with an energy gap larger than for the neutral CB
Computational chemistry for graphene-based energy applications: progress and challenges
YesResearch in graphene-based energy materials is a rapidly growing area. Many graphene-based energy applications involve interfacial processes. To enable advances in the design of these energy materials, such that their operation, economy, efficiency and durability is at least comparable with fossil-fuel based alternatives, connections between the molecular-scale structure and function of these interfaces are needed. While it is experimentally challenging to resolve this interfacial structure, molecular simulation and computational chemistry can help bridge these gaps. In this Review, we summarise recent progress in the application of computational chemistry to graphene-based materials for fuel cells, batteries, photovoltaics and supercapacitors. We also outline both the bright prospects and emerging challenges these techniques face for application to graphene-based energy materials in future.vesk
Nanoscale Friction Switches: Friction Modulation of Monomolecular Assemblies Using External Electric Fields
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