Two-Component GW Calculations: Cubic Scaling Implementation and Comparison of Vertex-Corrected and Partially Self-Consistent GW Variants

Journal of Chemical Theory and Computation, Journal Year: 2023, Volume and Issue: 19(17), P. 5958 - 5976

Published: Aug. 18, 2023

We report an all-electron, atomic orbital (AO)-based, two-component (2C) implementation of the GW approximation (GWA) for closed-shell molecules. Our algorithm is based on space-time formulation GWA and uses analytical continuation (AC) self-energy, pair-atomic density fitting (PADF) to switch between AO auxiliary basis. By calculating dynamical contribution self-energy at a quasi-one-component level, our 2C-GW only about factor 2-3 slower than in scalar relativistic case. Additionally, we present 2C simplest vertex correction statically screened G3W2 correction. Comparison first ionization potentials (IPs) set 67 molecules with heavy elements (a subset SOC81 set) calculated against results from WEST code reveals mean absolute deviations (MAD) around 70 meV G0W0@PBE G0W0@PBE0. check accuracy AC treatment by comparison full-frequency calculations, which shows that absence multisolution cases, errors due are minor. This implies main sources observed both implementations different single-particle bases pseudopotential code. Finally, assess performance some (partially self-consistent) variants calculation IPs vertical experimental reference values. G0W0@PBE0 (25% exact exchange) G0W0@BHLYP (50% perform best 200 meV. Explicit spin-orbit effects level crucial systematic agreement experiment. On other hand, eigenvalue-only self-consistent (evGW) quasi-particle (qsGW) significantly overestimate IPs. Perturbative corrections increase therefore improve experiment cases where G0W0 alone underestimates With MAD 140 meV, 2C-G0W0@PBE0 +

Language: Английский

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The Best Models of Bodipy’s Electronic Excited State: Comparing Predictions from Various DFT Functionals with Measurements from Femtosecond Stimulated Raman Spectroscopy

The Journal of Physical Chemistry A, Journal Year: 2023, Volume and Issue: 127(39), P. 8238 - 8251

Published: Sept. 26, 2023

Density functional theory (DFT) and time-dependent DFT (TD-DFT) are pivotal approaches for modeling electronically excited states of molecules. However, choosing a exchange-correlation (XCF) among the myriad alternatives is an overwhelming task that can affect interpretation results lead to erroneous conclusions. The performance these XCFs describe excited-state properties often addressed by comparing them with high-level wave function methods or experimentally available vertical excitation energies; however, this limited analysis relies on evaluation single point in potential energy surface (PES). Different strategies have been proposed but difficulty accessing electronic properties. In work, we tested 12 different TD-DFT Bodipy (2,6-diethyl-1,3,5,7-tetramethyl-8-phenyldipyrromethene difluoroborate). We compare those resonance Raman spectra collected using femtosecond stimulated spectroscopy (FSRS). By simultaneously fitting absorption spectrum, fluorescence all profiles within independent mode displaced harmonic oscillator (IMDHO) formalism, PES at Franck-Condon (FC) region determine solvent intramolecular reorganization after relaxation. This allows direct comparison output experimental observables. Our reveals energies might not be good criterion best XCF given molecular system FSRS opens up new way benchmark fluorescent dyes.

Language: Английский

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Cost-Effective Approach for Modeling of Multiresonant Thermally Activated Delayed Fluorescence Emitters

Journal of Chemical Theory and Computation, Journal Year: 2023, Volume and Issue: 19(24), P. 9290 - 9301

Published: Dec. 14, 2023

Multiresonant thermally activated delayed fluorescence (MR-TADF) emitters have recently attracted great interest for application in organic light-emitting diodes due to their remarkable electroluminescent efficiency and narrow emission spectra. It is therefore essential establish computational methodologies that can accurately model the excited states of these materials at manageable costs. With regard MR-TADF design associated photophysics, previous works highlighted importance wave function-based methods, much higher costs, over traditional time-dependent density functional theory approach. Herein, we employ two independent techniques built on different quantum mechanical frameworks, highly correlated STEOM-DLPNO-CCSD range-separated double hybrid functional, TD-B2PLYP, investigate performance predicting state energies emitters. We demonstrate a mean absolute deviation (MAD) ∼0.06 eV ΔEST compared experimental measurements across large pool chemically diverse molecules. Furthermore, both methods yield superior MAD estimating S1 T1 earlier reported SCS-CC2 computed values [J. Chem. Theory Comput.2022, 18, 4903]. The short-range charge-transfer nature low-lying fwhm values, hallmarks this class emitters, are precisely captured by approaches. Finally, show transferability robustness rates radiative nonradiative events with adequate agreement against measurements. Implementing cost-effective approaches poised streamline identification evaluation potential significantly reducing reliance costly laboratory synthesis characterization processes.

Language: Английский

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Exploring the Theoretical Foundations of Thermally Activated Delayed Fluorescence (TADF) Emission: A Comprehensive TD‐DFT Study on Phenothiazine Systems

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(20)

Published: Feb. 7, 2024

This study conducts a thorough theoretical investigation of Thermally Activated Delayed Fluorescence (TADF) in phenothiazine-based systems, examining ten molecular configurations recognized experimentally as TADF-active. Employing Time-Dependent Density Functional Theory (TD-DFT), our analysis spans the singlet-triplet energy gaps (ΔE

Language: Английский

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Inverted Lowest Singlet and Triplet Excitation Energy Ordering of Graphitic Carbon Nitride Flakes

The Journal of Physical Chemistry Letters, Journal Year: 2023, Volume and Issue: 14(49), P. 10910 - 10919

Published: Nov. 30, 2023

In organic light-emitting diodes (OLEDs), only 25% of electrically generated excitons are in a singlet state, S1, and the remaining 75% triplet T1. thermally activated delayed fluorescence (TADF) chromophores transition from nonradiative T1 state to radiative S1 can be activated, which improves efficiency OLEDs. Chromophores with inverted energy ordering states, < T1, superior TADF chromophores, thanks absence an barrier for S1. We benchmark performance time-dependent density functional theory using different exchange-correlation functionals find that scaled long-range corrected double-hybrid correctly predict singlet–triplet gaps N-substituted phenalene derivatives. then show is intrinsic property graphitic carbon nitride flakes. A design strategy new proposed. The color emitted light fine-tuned through flake size amine substitution on vertices.

Language: Английский

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C3 Substituted Naphthalimide Derivatives as Promising TADF Emitters: Effect of Donor Strength Revealed by Computational Studies

Advanced Theory and Simulations, Journal Year: 2025, Volume and Issue: unknown

Published: March 3, 2025

Abstract Thermally activated delayed fluorescence (TADF) emitters are pivotal in enhancing the electroluminescence efficiency of organic light‐emitting diodes (OLEDs) by enabling effective utilization triplet excitons. Emitters based on naphthalimide (NI) have not received much attention, particularly C3 substituted variants. In this study, a potential TADF molecule NI‐AZB featuring 10‐mesityl‐5,10‐dihydrodibenzo[b,e][1,4]azaborinine (AZB) as donor is shortlisted after rigorous consideration several similar derivatives possessing donors such carbazole, dimethylacridine, phenoxazine, and phenothiazine. Computational analyses indicate that exhibits small singlet‐triplet energy gap, promising radiative decay rates, moderate spin‐orbit coupling, substantial reverse intersystem crossing (rISC) rates. The S 1 state charge‐transfer (CT) nature, while T localized excitation (LE), facilitating enhanced coupling rISC Additionally, absorbs UV region, suggesting its blue‐emitting material for OLED devices. Furthermore, it observed substitution at C4 core enhances CT character, leading to higher rates but reduced Conversely, diminishes resulting increased maintaining These insights underscore importance optimizing properties naphthalimide‐based applications.

Language: Английский

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PAH101: A GW+BSE Dataset of 101 Polycyclic Aromatic Hydrocarbon (PAH) Molecular Crystals

Scientific Data, Journal Year: 2025, Volume and Issue: 12(1)

Published: April 23, 2025

Abstract The excited-state properties of molecular crystals are important for applications in organic electronic devices. G W approximation and Bethe-Salpeter equation ( +BSE) is the state-of-the-art method calculating crystalline solids with periodic boundary conditions. We present PAH101 dataset +BSE calculations 101 polycyclic aromatic hydrocarbons (PAHs) up to ~500 atoms unit cell. To best our knowledge, this first crystals. data records include quasiparticle band structure, fundamental gap, static dielectric constant, singlet exciton energy (optical gap), triplet energy, function, optical absorption spectra light polarized along three lattice vectors. can be used (i) discover materials desired electronic/optical properties, (ii) identify correlations between DFT quantities, (iii) train machine learned models help discovery efforts.

Language: Английский

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Relating Design and Optoelectronic Properties of 1,4-Dihydropyrrolo[3,2-b]pyrroles Bearing Biphenyl Substituents

The Journal of Physical Chemistry B, Journal Year: 2023, Volume and Issue: 127(33), P. 7352 - 7360

Published: Aug. 10, 2023

Understanding the influence of peripheral functionality on optoelectronic properties conjugated materials is an important task for continued development chromophores myriad applications. Here, π-extended 1,4-dihydropyrrolo[3,2-b]pyrrole (DHPP) with varying electron-donating or electron-withdrawing capabilities were synthesized via Suzuki cross-coupling reactions, and was elucidated. First, display distinct differences in UV–vis absorbance spectra measured spectroscopy addition to changes onset oxidation cyclic voltammetry differential pulse voltammetry. Solution studies found that variations -withdrawing result different profiles radical cations correspond quantifiably colors. In fundamental insights into molecular design DHPP their properties, two high-contrast electrochromism, which makes them potentially compelling electronic devices. Overall, this study represents ability fine-tune neutral oxidized states expands understanding structure–property relationships will guide DHPP-based materials.

Language: Английский

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Theoretical study on the efficiency of new organic dyes based on (E)-2-(2-(thiophen-3-yl)vinyl)-1,1′-bipyrrole as dye-sensitized solar cell sensitizers

ChemPhysMater, Journal Year: 2024, Volume and Issue: 3(4), P. 440 - 450

Published: July 20, 2024

Dye-sensitized solar cells (DSSCs) have gained critical importance as a leading emerging photovoltaic technology for low-cost power generation due to their simple production, light weight, applicability the development of flexible devices, and use abundant inexpensive materials, including advantageous metal-free organic dyes. In this context, continuation our work on DSSCs, theoretical examination using density functional theory (DFT) time-dependent (TD-DFT) was conducted evaluate performance eight new Each dye contains an electron donor group ((E)-2-(2-(thiophen-3-yl)vinyl)-1,1′-bipyrrole), acceptor (cyanoacrylic acid (CCA)), four auxiliary donor/acceptor groups, i.e., 3,4-ethylenedioxythiophene (EDOT), furan/benzothiadiazole (BTZ), diketopyrrolopyrrole (DPP) linked π-conjugated bridges such styrene or thiophene. We calculated several parameters each dye, EHOMO, ELUMO, Egap, λmax, Eex, pen-circuit photovoltage (VOC), harvesting efficiency (LHE), regeneration driving force (ΔGreg), injection (ΔGinject), excitation lifetime (τ) determine dye. The results showed that dyes exhibited good remarkable energy-conversion efficiencies. Additionally, all investigated posed promising candidates effective DSSC sensitizers, particularly M6, which contained styrene-linked EDOT group.

Language: Английский

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Computational Discovery of Intermolecular Singlet Fission Materials Using Many-Body Perturbation Theory

The Journal of Physical Chemistry C, Journal Year: 2024, Volume and Issue: 128(19), P. 7841 - 7864

Published: May 1, 2024

Intermolecular singlet fission (SF) is the conversion of a photogenerated exciton into two triplet excitons residing on different molecules. SF has potential to enhance efficiency solar cells by harvesting charge carriers from one high-energy photon, whose surplus energy would otherwise be lost heat. The development commercial SF-augmented modules hindered limited selection molecular crystals that exhibit intermolecular in solid state. Computational exploration may accelerate discovery new materials. GW approximation and Bethe–Salpeter equation (GW+BSE) within framework many-body perturbation theory current state-of-the-art method for calculating excited-state properties with periodic boundary conditions. In this Review, we discuss usage GW+BSE assess candidate materials as well its combination low-cost physical or machine learned models workflows. We demonstrate three successful strategies materials: (i) functionalization known tune their properties, (ii) finding polymorphs improved crystal packing, (iii) exploring classes addition, are proposed here, which have not been published previously.

Language: Английский

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