Earth Mover’s Distance as a Metric to Evaluate the Extent of Charge Transfer in Excitations Using Discretized Real-Space Densities DOI
Zhe Wang, Jiashu Liang, Martin Head‐Gordon

et al.

Journal of Chemical Theory and Computation, Journal Year: 2023, Volume and Issue: 19(21), P. 7704 - 7714

Published: Nov. 3, 2023

This paper presents a novel theoretical measure, μEMD, based on the earth mover's distance (EMD), for quantifying density shift caused by electronic excitations in molecules. As input, EMD metric uses only discretized ground- and excited-state electron densities real space, rendering it compatible with almost all structure methods used to calculate excited states. The is compared against other popular metrics describing extent of electron-hole separation wide range states (valence, Rydberg, charge transfer, etc.). results showcase metric's effectiveness across excitation types suggest that useful as an additional tool characterize excitations. study also reveals μEMD can function promising diagnostic predicting failure pure exchange-correlation functionals. Specifically, we show statistical relationships among functional-driven errors, exact exchange content within functional, magnitude values.

Language: Английский

Revisiting the Performance of Time-Dependent Density Functional Theory for Electronic Excitations: Assessment of 43 Popular and Recently Developed Functionals from Rungs One to Four DOI
Jiashu Liang, Xintian Feng, Diptarka Hait

et al.

Journal of Chemical Theory and Computation, Journal Year: 2022, Volume and Issue: 18(6), P. 3460 - 3473

Published: May 9, 2022

In this paper, the performance of more than 40 popular or recently developed density functionals is assessed for calculation 463 vertical excitation energies against large and accurate QuestDB benchmark set. For purpose, Tamm-Dancoff approximation offers a good balance between computational efficiency accuracy. The ωB97X-D BMK are found to offer best overall with root-mean square error (RMSE) around 0.27 eV, better computationally demanding CIS(D) wave function method RMSE 0.36 eV. results also suggest that Jacob's ladder still holds time-dependent functional theory energies, though hybrid meta generalized-gradient approximations (meta-GGAs) not generally GGAs. Effects basis set convergence, gauge invariance correction meta-GGAs, nonlocal correlation (VV10) studied, practical recommendations provided.

Language: Английский

Citations

121
Density-functional theory for electronic excited states DOI
John M. Herbert

Elsevier eBooks, Journal Year: 2023, Volume and Issue: unknown, P. 69 - 118

Published: Jan. 1, 2023

Language: Английский

Citations

27
Review on the DFT computation of bulk heterojunction and dye-sensitized organic solar cell properties DOI
Nathália M. P. Rosa, Itamar Borges

Journal of Molecular Modeling, Journal Year: 2025, Volume and Issue: 31(3)

Published: Feb. 13, 2025

Language: Английский

Citations

1
Reply to the ‘Comment on “Designing potentially singlet fission materials with an anti-Kasha behaviour”’ by K. Jindal, A. Majumdar and R. Ramakrishnan, Phys. Chem. Chem. Phys., 2025, 27, DOI: 10.1039/D4CP02863E DOI Creative Commons
Ricardo Pino‐Rios, Rodrigo Báez‐Grez, Dariusz W. Szczepanik

et al.

Physical Chemistry Chemical Physics, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

In this reply, we argue that the time-dependent density functional theory (TD-DFT) yields plausible results are consistent with high-level ab initio calculations and experimental findings.

Language: Английский

Citations

1
Simplified Tuning of Long-Range Corrected Time-Dependent Density Functional Theory DOI

Aniket Mandal,

John M. Herbert

The Journal of Physical Chemistry Letters, Journal Year: 2025, Volume and Issue: unknown, P. 2672 - 2680

Published: March 6, 2025

Range-separated hybrid functionals have dramatically improved the description of charge-transfer excitations in time-dependent density functional theory (TD-DFT), especially when range-separation parameter is adjusted order to satisfy ionization energy (IE) criterion, εHOMO = -IE. However, this "optimal tuning" procedure molecule-specific, inconvenient, expensive for large systems, and problematic extended or periodic systems. Here, we consider an alternative known as global density-dependent (GDD) tuning, which sets automated way based on properties exchange hole. In small molecules, find that long-range corrected with either IE GDD tuning afford remarkably similar TD-DFT excitation energies, both valence excitations. more efficient well-behaved even It provides a black-box solution optimal-tuning problem can replace many applications TD-DFT.

Language: Английский

Citations

1
Visualizing and characterizing excited states from time-dependent density functional theory DOI
John M. Herbert

Physical Chemistry Chemical Physics, Journal Year: 2023, Volume and Issue: 26(5), P. 3755 - 3794

Published: Dec. 12, 2023

Time-dependent density functional theory (TD-DFT) is the most widely-used electronic structure method for excited states, due to a favorable combination of low cost and semi-quantitative accuracy in many contexts, even if there are well recognized limitations. This Perspective describes various ways which states from TD-DFT calculations can be visualized analyzed, both qualitatively quantitatively. includes not just orbitals densities but also well-defined statistical measures electron-hole separation Frenkel-type exciton delocalization. Emphasis placed on mathematical connections between methods that have often been discussed separately. Particular attention paid charge-transfer diagnostics, provide indicators when may trustworthy its categorical failure describe long-range electron transfer. Measures size charge directly connected underlying transition recommended over more

Language: Английский

Citations

17
Orbital-Optimized Versus Time-Dependent Density Functional Calculations of Intramolecular Charge Transfer Excited States DOI
Elli Selenius, Alec Elías Sigurðarson, Yorick L. A. Schmerwitz

et al.

Journal of Chemical Theory and Computation, Journal Year: 2024, Volume and Issue: 20(9), P. 3809 - 3822

Published: May 2, 2024

The performance of time-independent, orbital-optimized calculations excited states is assessed with respect to charge transfer excitations in organic molecules comparison the linear-response time-dependent density functional theory (TD-DFT) approach. A direct optimization method converge on saddle points electronic energy surface used carry out local approximation (LDA) and generalized gradient (GGA) functionals PBE BLYP for a set 27 15 molecules. time-independent approach fully variational provides relaxed state electron from which extent quantified. TD-DFT are generally found provide larger distances compared calculations, even when including orbital relaxation effects Z-vector method. While error excitation relative theoretical best estimates increase up ca. −2 eV TD-DFT, no correlation observed LDA GGA mean absolute ∼0.7 eV, outperforming both global hybrid long-range character. Orbital-optimized B3LYP range-separated CAM-B3LYP selection short- indicate that inclusion exact exchange has small effect distance, while it significantly improves energy, best-performing providing an typically around 0.15 eV.

Language: Английский

Citations

7
Benchmarking DFT-based excited-state methods for intermolecular charge-transfer excitations DOI Creative Commons
Nicola Bogo, Christopher J. Stein

Physical Chemistry Chemical Physics, Journal Year: 2024, Volume and Issue: 26(32), P. 21575 - 21588

Published: Jan. 1, 2024

Intermolecular charge-transfer is a highly important process in biology and energy-conversion applications where generated charges need to be transported over several moieties. However, its theoretical description challenging since the high accuracy required describe these excited states must accessible for calculations on large molecular systems. In this benchmark study, we identify reliable low-scaling computational methods task. Our reference results were obtained from accurate wavefunction that restrict size of density-functional theory based as can applied much larger Since targeting requires unambiguous classification an state, first analyze descriptors their reliability concerning intermolecular single out distance calculated variation electron density upon excitation (

Language: Английский

Citations

6
Recent Advances in Real-Time Time-Dependent Density Functional Theory Simulations of Plasmonic Nanostructures and Plasmonic Photocatalysis DOI Creative Commons

Connor J. Herring,

M. M. Montemore

ACS Nanoscience Au, Journal Year: 2023, Volume and Issue: 3(4), P. 269 - 279

Published: May 19, 2023

Plasmonic catalysis provides a possible means for driving chemical reactions under relatively mild conditions. Rational design of these systems is impeded by the difficulty in understanding electron dynamics and their interplay with reactions. Real-time, time-dependent density functional theory (RT-TDDFT) can provide dynamic information on excited states plasmonic systems, including those relevant to catalysis, at time scales length that are otherwise out reach many experimental techniques. Here, we discuss previous RT-TDDFT studies focusing recent work gains insight into catalysis. These plasmon dynamics, size effects role specific electronic states. Further, significant mechanisms underlying showing importance charge transfer between metal adsorbate states, as well local field enhancement, different systems.

Language: Английский

Citations

15
Ultrafast Spectroscopies of Nitrophenols and Nitrophenolates in Solution: From Electronic Dynamics and Vibrational Structures to Photochemical and Environmental Implications DOI Creative Commons

Sullivan Bailey-Darland,

Taylor D. Krueger, Chong Fang

et al.

Molecules, Journal Year: 2023, Volume and Issue: 28(2), P. 601 - 601

Published: Jan. 6, 2023

Nitrophenols are a group of small organic molecules with significant environmental implications from the atmosphere to waterways. In this work, we investigate series nitrophenols and nitrophenolates, contrasting

Language: Английский

Citations

13