3 research outputs found
Model Hamiltonian Analysis of Singlet Fission from First Principles
We
present an approach to accurately construct the few-state model
Hamiltonians for singlet fission processes on the basis of an ab initio
electronic structure method tailored to dimer wave functions, called
an active space decomposition strategy. In this method, the electronic
structure of molecular dimers is expressed in terms of a linear combination
of products of monomer states. We apply this method to tetracene and
pentacene, using monomer wave functions computed by the restricted
active space (RAS) method. Near-exact wave functions are computed
for π-electrons of dimers that contain up to 7 × 10<sup>12</sup> electronic configurations. Our product ansatz preserves
the diabatic picture of the minimal dimer model, allowing us to accurately
identify model Hamiltonians. The wave functions obtained from the
model Hamiltonians account for more than 99% of the total wave functions.
The resulting model Hamiltonians are shown to be converged with respect
to all the parameters in the model, and corroborate previously reported
coupling strengths
Scalable Synthesis and Characterization of Multilayer γ‑Graphyne, New Carbon Crystals with a Small Direct Band Gap
γ-Graphyne
is the most symmetric sp2/sp1 allotrope of carbon,
which can be viewed as graphene uniformly expanded
through the insertion of two-carbon acetylenic units between all the
aromatic rings. To date, synthesis of bulk γ-graphyne has remained
a challenge. We here report the synthesis of multilayer γ-graphyne
through crystallization-assisted irreversible cross-coupling polymerization.
A comprehensive characterization of this new carbon phase is described,
including synchrotron powder X-ray diffraction, electron diffraction,
lateral force microscopy, Raman spectroscopy, infrared spectroscopy,
and cyclic voltammetry. Experiments indicate that γ-graphyne
is a 0.48 eV band gap semiconductor, with a hexagonal a-axis spacing of 6.88 Ã… and an interlayer spacing of 3.48 Ã…,
which is consistent with theoretical predictions. The observed crystal
structure has an aperiodic sheet stacking. The material is thermally
stable up to 240 °C but undergoes transformation at higher temperatures.
While conventional 2D polymerization and reticular chemistry rely
on error correction through reversibility, we demonstrate that a periodic
covalent lattice can be synthesized under purely kinetic control.
The reported methodology is scalable and inspires extension to other
allotropes of the graphyne family
Scalable Synthesis and Characterization of Multilayer γ‑Graphyne, New Carbon Crystals with a Small Direct Band Gap
γ-Graphyne
is the most symmetric sp2/sp1 allotrope of carbon,
which can be viewed as graphene uniformly expanded
through the insertion of two-carbon acetylenic units between all the
aromatic rings. To date, synthesis of bulk γ-graphyne has remained
a challenge. We here report the synthesis of multilayer γ-graphyne
through crystallization-assisted irreversible cross-coupling polymerization.
A comprehensive characterization of this new carbon phase is described,
including synchrotron powder X-ray diffraction, electron diffraction,
lateral force microscopy, Raman spectroscopy, infrared spectroscopy,
and cyclic voltammetry. Experiments indicate that γ-graphyne
is a 0.48 eV band gap semiconductor, with a hexagonal a-axis spacing of 6.88 Ã… and an interlayer spacing of 3.48 Ã…,
which is consistent with theoretical predictions. The observed crystal
structure has an aperiodic sheet stacking. The material is thermally
stable up to 240 °C but undergoes transformation at higher temperatures.
While conventional 2D polymerization and reticular chemistry rely
on error correction through reversibility, we demonstrate that a periodic
covalent lattice can be synthesized under purely kinetic control.
The reported methodology is scalable and inspires extension to other
allotropes of the graphyne family