2 research outputs found
MoS<sub>2</sub> Quantum Dots: Effect of Hydrogenation on Surface Stability and H<sub>2</sub>S Release
We
employ density functional theory to investigate effects of hydrogenation
on the energetic stability and electronic properties of triangular
MoS<sub>2</sub> nanoclusters with S-edges. Excess edge sulfur atoms
relative to the bulk stoichiometry along the edges are passivated
by hydrogen atoms. We find that the hydrogen coverage for maximum
stability can be calculated by (<i>n</i> – 2)/2Â(<i>n</i> – 1), where <i>n</i> is the number of
S atoms along an edge. The energetics reveal a preference for the
zigzag arrangement of adsorbed hydrogen atoms on the edges. Our calculations
show vanishing HOMO–LUMO gaps mainly due to the presence of
dangling bonds at the edges and can be considered metal-like. We find
that the activation energy required to release H<sub>2</sub>S lies
in between 0.47 and 0.62 eV, and this value is in good agreement with
the recently reported experimental value
Empirical Relationship between Chemical Structure and Redox Properties: Mathematical Expressions Connecting Structural Features to Energies of Frontier Orbitals and Redox Potentials for Organic Molecules
A set of mathematical expressions
to predict redox potentials and
frontier orbital energy levels for organic molecules as a function
of structural features is proposed. This is achieved by using the
principal component regression method on reduction potential (<i>E</i><sub>red</sub>), oxidation potential (<i>E</i><sub>ox</sub>), highest occupied molecular orbital (HOMO), and lowest
unoccupied molecular orbital (LUMO) values calculated using density
functional theory (DFT) on a training set consisting of 77 547
molecules from PubChem database. The first set of expressions allows
prediction of <i>E</i><sub>red</sub>, <i>E</i><sub>ox</sub>, HOMO, and LUMO values using molecular fingerprints
alone with <i>R</i><sup>2</sup> of ca. 0.74, 0.82, 0.92,
and 0.85, respectively, which can be used for preliminary screening
of molecules before performing DFT calculations. In the second set
of expressions, when we include DFT-calculated HOMO and LUMO values
as additional descriptors, the <i>R</i><sup>2</sup> values
of <i>E</i><sub>ox</sub> and <i>E</i><sub>red</sub> predictions increase to 0.91 and 0.90, respectively. This more accurate
approach for redox potential predictions is still significantly more
computationally efficient compared to DFT calculations of redox potentials.
The potential of these approaches is demonstrated by using the examples
of polyacenes and quinoxaline family of molecules. These empirical
relations are ideally suited for high-throughput screening for a variety
of optoelectronic applications. The resultant tool, QSROAR, is made
available at https://github.com/piyushtagade/qsroar_version2