Structural and excited-state properties of oligoacene crystals from first principles

Abstract

Molecular crystals are a prototypical class of van der Waals (vdW) bound organic materials with excited state properties relevant for optoelectronics applications. Predicting the structure and excited state properties of molecular crystals presents a challenge for electronic structure theory, as standard approximations to density functional theory (DFT) do not capture long range vdW dispersion interactions and do not yield excited state properties. In this work, we use a combination of DFT including vdW forces) using both non local correlation functionals and pair wise correction methods (together with many body perturbation theory (MBPT) to study the geometry and excited states, respectively, of the entire series of oligoacene crystals, from benzene to hexacene. We find that vdW methods can predict lattice constants within 1 percent of the experimental measurements, on par with the previously reported accuracy of pairwise approximations for the same systems. We further find that excitation energies are sensitive to geometry, but if optimized geometries are used MBPT can yield excited state properties within a few tenths of an eV from experiment. We elucidate trends in MBPT computed charged and neutral excitation energies across the acene series and discuss the role of common approximations used in MBPT.

References in corpus (36)

• Quantum ESPRESSO: a modular and open-source software project for quantum simulations of materials
• Restoring the density-gradient expansion for exchange in solids and surfaces
• Generalized gradient approximation for solids and their surfaces
• Van der Waals Density Functional for General Geometries
• Maximally-localized generalized Wannier functions for composite energy bands
• A Higher-Accuracy van der Waals Density Functional
• Pseudopotentials for high-throughput DFT calculations
• Ab initio pseudopotentials for electronic structure calculations of poly-atomic systems using density-functional theory
• Nonlocal van der Waals density functional: The simpler the better
• Perspective: Advances and challenges in treating van der Waals dispersion forces in density functional theory
• BerkeleyGW: A Massively Parallel Computer Package for the Calculation of the Quasiparticle and Optical Properties of Materials and Nanostructures
• Quasiparticle Self-Consistent GW Theory
• Renormalization of Molecular Electronic Levels at Metal-Molecule Interfaces
• van der Waals forces in density functional theory: The vdW-DF method
• An exchange functional that tests the robustness of the plasmon description of the van der Waals density functional
• First-principles GW calculations for fullerenes, porphyrins, phtalocyanine, and other molecules of interest for organic photovoltaic applications
• Microscopic theory of singlet exciton fission. II. Application to pentacene dimers and the role of superexchange
• Fully selfconsistent GW calculations for molecules
• Solid-state optical absorption from optimally-tuned time-dependent range-separated hybrid density functional theory
• Optical excitations in organic molecules, clusters and defects studied by first-principles Green's function methods
• Quasiparticle and Optical Spectroscopy of Organic Semiconductors Pentacene and PTCDA from First Principles
• A Benchmark of GW Methods for Azabenzenes: Is the GW Approximation Good Enough?
• Charge-transfer excitations in molecular donor-acceptor complexes within the many-body Bethe-Salpeter approach
• Coulomb-hole summations and energies for GW calculations with limited number of empty orbitals: a modified static remainder approach
• Exciton-plasmon states in nanoscale materials: breakdown of the Tamm-Dancoff approximation
• van der Waals density functionals built upon the electron-gas tradition: Facing the challenge of competing interactions
• Time-dependent density functional study of the electronic spectra of oligoacenes in the charge states -1, 0, +1, and +2
• An analysis of van der Waals density functional components: Binding and corrugation of benzene and C60 on boron nitride and graphene
• Phonons and structures of tetracene polymorphs at low temperature and high pressure
• Interpretation of van der Waals density functionals
• Quantitative Molecular Orbital Energies within a $G_0{W}_0$ Approximation
• van der Waals density functional calculations of binding in molecular crystals
• Spectra and total energies from self-consistent many-body perturbation theory
• Structure and binding in crystals of cage-like molecules: hexamine and platonic hydrocarbons
• Effects of self-consistency and plasmon-pole models on GW calculations for closed-shell molecules
• Polymorphism, phonon dynamics and carrier-phonon coupling in pentacene

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• Charge Transport in Organic Molecular Semiconductors from First Principles: The Band-Like Hole Mobility in Naphthalene Crystal
• Accurate description of charged excitations in molecular solids from embedded many-body perturbation theory
• Origins of singlet fission in solid pentacene from an ab initio Green's-function approach
• Physically inspired deep learning of molecular excitations and photoemission spectra
• Triplet-Tuning: A Novel Family of Non-Empirical Exchange-Correlation Functionals
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• Signatures of van der Waals binding: a coupling-constant scaling analysis
• Extent of Fock-exchange mixing for a hybrid van der Waals density functional?
• Energy scaling law for nanostructured materials
• Efficient treatment of molecular excitations in the liquid phase environment via stochastic many-body theory
• Solving the Bethe-Salpeter Equation on a Subspace: Approximations and Consequences for Low-dimensional Materials
• vdW-DF-ahcx: a range-separated van der Waals density functional hybrid
• Modeling the electronic structure of organic materials: A solid-state physicist's perspective
• Polymorphism in $\alpha$-sexithiophene crystals: Relative stability and transition path
• Polarization Resolved Optical Excitation of Charge-Transfer Excitons in PEN:PFP Co-Crystalline Films: Limits of Non-Periodic Modelling
• Microscopic Insight into the Electronic Structure of BCF-Doped Oligothiophenes from \textit{Ab initio} Many-Body Theory
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