Assessing the Role of Intermolecular Interactions in a Perylene-Based Nanowire Using First-Principles Many-Body Perturbation Theory

Huang, Tianlun; Lewis, D. Kirk; Sharifzadeh, Sahar

doi:10.1021/acs.jpclett.9b00800

Cited by 12 publications

(11 citation statements)

References 69 publications

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“…π-stacked interacting molecules additionally differ from monomeric ones because intermolecular electronic coupling results in the presence of multiple low-energy states that contribute to the peaks in the absorption spectra of molecular stacks. ,− For the class of molecules studied here, we have previously shown strong intermolecular electronic coupling. ,, We predict that there are two low-energy electronic states close in energy for P2 and four low-energy electronic states close in energy for P3. For all of the structures extracted from MD, these nearly degenerate states are within 0.3 eV, well within the energy window of the experimental spectra.…”

Section: Resultsmentioning

confidence: 74%

“…10,56−61 For the class of molecules studied here, we have previously shown strong intermolecular electronic coupling. 40,41,62 We predict that there are two lowenergy electronic states close in energy for P2 and four lowenergy electronic states close in energy for P3. For all of the structures extracted from MD, these nearly degenerate states are within 0.3 eV, well within the energy window of the experimental spectra.…”

Section: ■ Results and Discussionmentioning

confidence: 87%

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Accurate First-Principles Calculation of the Vibronic Spectrum of Stacked Perylene Tetracarboxylic Acid Diimides

et al. 2020

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π-stacked organic electronic materials are tunable light absorbers with many potential applications in optoelectronics. The optical properties of such molecules are highly dependent on the nature and energy of electron–hole pairs or excitons formed upon light absorption, which in turn are determined by intra- and intermolecular electronic and vibrational excitations. Here, we present a first-principles approach for describing the optical spectrum of stacked organic molecules with strong vibronic coupling. For stacked perylene tetracarboxylic acid diimides, we describe optical excitations by using the time-dependent density functional theory with a Franck–Condon Herzberg–Teller approximation of vibronic effects and validate our approach with comparison to experimental ultraviolet–visible (UV–vis) absorption measurements of solvated model systems. We determine that for larger macromolecules, unlike for single molecules, the sampling of the ground-state potential energy surface significantly influences the optical absorption spectrum. We account for this effect by applying our analysis to ∼100 structures extracted from equilibrated molecular dynamics simulations and averaging the optical spectrum over the entire ensemble. Additionally, we demonstrate that intermolecular electronic coupling within the stacks results in multiple low-energy electronically excited states that all contribute to the optical spectrum. This study provides a computationally feasible recipe for describing the spectroscopic properties of stacked organic chromophores via first-principles density functional theory.

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Section: Resultsmentioning

confidence: 74%

Section: ■ Results and Discussionmentioning

confidence: 87%

Accurate First-Principles Calculation of the Vibronic Spectrum of Stacked Perylene Tetracarboxylic Acid Diimides

et al. 2020

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“…Although thermal diffuse scattering is fundamentally related to the phonon properties of the crystal, this concept reinforces the use of ZG displacements for the evaluation of temperature-dependent electronic and optical properties of solids, as attested in Refs. [24,25,[57][58][59][60][61][62][63][64][65][66][67][68][69][70]. It is also evident that ZG calculations can capture accurately all terms in the Taylor expansion of the observable of interest, and thus can serve as a tool for the assessment of multi-phonon effects, including electron-multi-phonon coupling.…”

Section: A Monolayer Mos2mentioning

confidence: 99%

Multi-phonon diffuse scattering in solids from first-principles: Application to layered crystals and 2D materials

Zacharias,

Seiler,

Caruso

et al. 2021

Preprint

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Time-resolved diffuse scattering experiments have gained increasing attention due to their potential to reveal non-equilibrium dynamics of crystal lattice vibrations with full momentum resolution. Although progress has been made in interpreting experimental data on the basis of one-phonon scattering, understanding the role of individual phonons can be sometimes hindered by multi-phonon excitations. In Ref. [arXiv:2103.10108] we have introduced a rigorous approach for the calculation of the all-phonon inelastic scattering intensity of solids from first-principles. In the present work, we describe our implementation in detail and show that multi-phonon interactions are captured efficiently by exploiting translational and time-reversal symmetries of the crystal. We demonstrate its predictive power by calculating the diffraction patterns of monolayer molybdenum disulfide (MoS2), bulk MoS2, and black phosphorus (bP), and we obtain excellent agreement with our measurements of thermal electron diffuse scattering. Remarkably, our results show that multi-phonon excitations dominate in bP across multiple Brillouin zones, while in MoS2 play a less pronounced role. We expand our analysis for each system and we examine the effect of individual atomic and interatomic vibrational motion on the diffuse scattering signals. Our findings indicate that distinct features are explained by the collective displacement of MoS and specific pairs of P atoms. We further demonstrate that the special displacement method reproduces the thermally distorted configuration which generates precisely the all-phonon diffraction pattern. The present methodology opens the way for high-throughput calculations of the scattering intensity in crystals and the accurate interpretation of static and time-resolved diffuse scattering experiments.

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“…The relative computational ease of this approach allows for it to be coupled with methods that include many-body physics in describing electronic excitations, such as many-body perturbation theory (MBPT) . 39,40 In this case, the limitation on the calculation is MBPT and not the electron− phonon calculation, such that this phenomonon can be studied in large and complex systems such as 2D materials and their interfaces.…”

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confidence: 99%

“…In practice, in this approach one computes a single frozen atomic structure that captures the quantum thermal average of phonon-induced band renormalization and phonon-assisted transitions in the optical absorption spectrum. The relative computational ease of this approach allows for it to be coupled with methods that include many-body physics in describing electronic excitations, such as many-body perturbation theory (MBPT) . , In this case, the limitation on the calculation is MBPT and not the electron–phonon calculation, such that this phenomonon can be studied in large and complex systems such as 2D materials and their interfaces.…”

mentioning

confidence: 99%

Exciton–Phonon Interactions in Monolayer Germanium Selenide from First Principles

Huang

Zacharias

Lewis

et al. 2021

J. Phys. Chem. Lett.

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We investigate from first principles exciton–phonon interactions in monolayer germanium selenide, a direct gap two-dimensional semiconductor. By combining the Bethe–Salpeter approach and the special displacement method, we explore the phonon-induced renormalization of the exciton wave functions, excitation energies, and oscillator strengths. We determine a renormalization of the optical gap of 0.1 eV at room temperature, which results from the coupling of the exciton with both acoustic and optical phonons, with the strongest coupling to optical phonons at ∼100 cm–1. We also find that the exciton–phonon interaction is similar between monolayer and bulk GeSe. Overall, we demonstrate that the combination of many-body perturbation theory and special displacements offers a new route to investigate electron–phonon couplings in excitonic spectra, the resulting band gap renormalization, and the nature of phonons that couple to the exciton.

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Assessing the Role of Intermolecular Interactions in a Perylene-Based Nanowire Using First-Principles Many-Body Perturbation Theory

Cited by 12 publications

References 69 publications

Accurate First-Principles Calculation of the Vibronic Spectrum of Stacked Perylene Tetracarboxylic Acid Diimides

Accurate First-Principles Calculation of the Vibronic Spectrum of Stacked Perylene Tetracarboxylic Acid Diimides

Multi-phonon diffuse scattering in solids from first-principles: Application to layered crystals and 2D materials

Exciton–Phonon Interactions in Monolayer Germanium Selenide from First Principles

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