24,224 research outputs found
First-principles molecular structure search with a genetic algorithm
The identification of low-energy conformers for a given molecule is a
fundamental problem in computational chemistry and cheminformatics. We assess
here a conformer search that employs a genetic algorithm for sampling the
low-energy segment of the conformation space of molecules. The algorithm is
designed to work with first-principles methods, facilitated by the
incorporation of local optimization and blacklisting conformers to prevent
repeated evaluations of very similar solutions. The aim of the search is not
only to find the global minimum, but to predict all conformers within an energy
window above the global minimum. The performance of the search strategy is: (i)
evaluated for a reference data set extracted from a database with amino acid
dipeptide conformers obtained by an extensive combined force field and
first-principles search and (ii) compared to the performance of a systematic
search and a random conformer generator for the example of a drug-like ligand
with 43 atoms, 8 rotatable bonds and 1 cis/trans bond
Density Functional Theory screening of gas-treatment strategies for stabilization of high energy-density lithium metal anodes
To explore the potential of molecular gas treatment of freshly cut lithium
foils in non-electrolyte based passivation of high energy-density Li anodes,
density functional theory (DFT) has been used to study the decomposition of
molecular gases on metallic lithium surfaces. By combining DFT geometry
optimization and Molecular Dynamics, the effects of atmospheric (N2, O2, CO2)
and hazardous (F2, SO2) gas decomposition on Li(bcc) (100), (110), and (111)
surfaces on relative surface energies, work functions, and emerging electronic
and elastic properties are investigated. The simulations suggest that exposure
to different molecular gases can be used to induce and control reconstructions
of the metal Li surface and substantial changes (up to over 1 eV) in the work
function of the passivated system. Contrary to the other considered gases,
which form metallic adlayers, SO2 treatment emerges as the most effective in
creating an insulating passivation layer for dosages <= 1 mono-layer. The
substantial Li->adsorbate charge transfer and adlayer relaxation produce marked
elastic stiffening of the interface, with the smallest change shown by
nitrogen-treated adlayers
Applied Symmetry for Crystal Structure Prediction
This thesis presents an original open-source Python package called PyXtal (pronounced pi-crystal ) that generates random symmetric crystal structures for use in crystal structure prediction (CSP). The primary advantage of PyXtal over existing structure generation tools is its unique symmetrization method. For molecular structures, PyXtal uses an original algorithm to determine the compatibility of molecular point group symmetry with Wyckoff site symmetry. This allows the molecules in generated structures to occupy special Wyckoff positions without breaking the structure\u27s symmetry. This is a new feature which increases the space of search-able structures and in turn improves CSP performance.
It is shown that using already-symmetric initial structures results in a higher probability of finding the lowest-energy structure. Ultimately, this lowers the computational time needed for CSP. Structures can be generated for any symmetry group of 0, 1, 2, or 3 dimensions of periodicity. Either atoms or rigid molecules may be used as building blocks. The generated structures can be optimized with VASP, LAMMPS, or other computational tools. Additional options are provided for the lattice and inter-atomic distance constraints. Results for carbon and silicon crystals, water ice crystals, and molybdenum clusters are presented as usage examples
Ab Initio Studies of Cellulose I: Crystal Structure, Intermolecular Forces, and Interactions with Water
We have studied the structural, energetic, and electronic properties of crystalline cellulose I using first-principles density functional theory (DFT) with semiempirical dispersion corrections. The predicted crystal structures of both Iα and Iβ phases agree well with experiments and are greatly improved over those predicted by DFT within the local and semilocal density approximations. The cohesive energy is analyzed in terms of interchain and intersheet interactions, which are calculated to be of similar magnitude. Both hydrogen bonding and van der Waals (vdW) dispersion forces are found to be responsible for binding cellulose chains together. In particular, dispersion corrections prove to be indispensable in reproducing the equilibrium intersheet distance and binding strength; however, they do not improve the underestimated hydrogen bond length from DFT. The computed energy gaps of crystalline cellulose are 5.7 eV (Iα) and 5.4 eV (Iβ), whereas localized surface states appear within the gap for surfaces. The interaction of cellulose with water is studied by investigating the adsorption of a single water molecule on the hydrophobic Iβ(100) surface. The formation of hydrogen bond at the water/cellulose interface is shown to depend sensitively on the adsorption site for example above the equatorial hydroxyls or the CH moieties pointing out of the cellulose sheets. VdW dispersion interactions also contribute significantly to the adsorption energy
Toward transferable interatomic van der Waals interactions without electrons: The role of multipole electrostatics and many-body dispersion
We estimate polarizabilities of atoms in molecules without electron density,
using a Voronoi tesselation approach instead of conventional density
partitioning schemes. The resulting atomic dispersion coefficients are
calculated, as well as many-body dispersion effects on intermolecular potential
energies. We also estimate contributions from multipole electrostatics and
compare them to dispersion. We assess the performance of the resulting
intermolecular interaction model from dispersion and electrostatics for more
than 1,300 neutral and charged, small organic molecular dimers. Applications to
water clusters, the benzene crystal, the anti-cancer drug
ellipticine---intercalated between two Watson-Crick DNA base pairs, as well as
six macro-molecular host-guest complexes highlight the potential of this method
and help to identify points of future improvement. The mean absolute error made
by the combination of static electrostatics with many-body dispersion reduces
at larger distances, while it plateaus for two-body dispersion, in conflict
with the common assumption that the simple correction will yield proper
dissociative tails. Overall, the method achieves an accuracy well within
conventional molecular force fields while exhibiting a simple parametrization
protocol.Comment: 13 pages, 8 figure
Development of a Transferable Reactive Force Field of P/H Systems: Application to the Chemical and Mechanical Properties of Phosphorene
ReaxFF provides a method to model reactive chemical systems in large-scale
molecular dynamics simulations. Here, we developed ReaxFF parameters for
phosphorus and hydrogen to give a good description of the chemical and
mechanical properties of pristine and defected black phosphorene. ReaxFF for
P/H is transferable to a wide range of phosphorus and hydrogen containing
systems including bulk black phosphorus, blue phosphorene, edge-hydrogenated
phosphorene, phosphorus clusters and phosphorus hydride molecules. The
potential parameters were obtained by conducting unbiased global optimization
with respect to a set of reference data generated by extensive ab initio
calculations. We extend ReaxFF by adding a 60{\deg} correction term which
significantly improves the description of phosphorus clusters. Emphasis has
been put on obtaining a good description of mechanical response of black
phosphorene with different types of defects. Compared to nonreactive SW
potential [1], ReaxFF for P/H systems provides a huge improvement in describing
the mechanical properties the pristine and defected black phosphorene and the
thermal stability of phosphorene nanotubes. A counterintuitive phenomenon is
observed that single vacancies weaken the black phosphorene more than double
vacancies with higher formation energy. Our results also show that mechanical
response of black phosphorene is more sensitive to defects for the zigzag
direction than for the armchair direction. Since ReaxFF allows straightforward
extensions to the heterogeneous systems, such as oxides, nitrides, ReaxFF
parameters for P/H systems build a solid foundation for the reactive force
field description of heterogeneous P systems, including P-containing 2D van der
Waals heterostructures, oxides, etc
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