Are all charge-transfer parameters created equally? A study of functional dependence and excited-state charge-transfer quantification across two dye families

Marshburn, Richard Drew; Ashley, Daniel C.; Curtin, Gregory M.; Sultana, Nadia; Liu, Chang; Vinueza, Nelson R.; Ison, Elon A.; Jakubı́ková, Elena

doi:10.1039/d1cp03383b

Cited by 4 publications

(2 citation statements)

References 59 publications

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“…Various LR-TDDFT errors have been rationalized by appeal to Λ or similar metrics. 135,243,296,297 The point at which CT character becomes a problem is dependent on the manner in which it is quantified, 298 and several alternative CT metrics have been suggested. [293][294][295][299][300][301][302][303][304][305] Ciofini and co-workers introduced a widely-used "D CT metric", 299 originally defined in a rather complicated way but which ultimately measures the distance between the centroids of ∆ρ elec (r) and ∆ρ hole (r).…”

Section: Description Of Charge Transfermentioning

confidence: 99%

Density Functional Theory for Electronic Excited States

Herbert¹

2022

Preprint

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This chapter provides a basic introduction to excited-state extensions of density functional theory (DFT), including time-dependent (TD-)DFT in both its linear-response and its explicitly time-dependent formulations. As applied to the Kohn-Sham DFT ground state, linear-response theory affords an eigenvaluetype problem for the excitation energies in a basis of singly-excited Slater determinants, and is widely known simply as "TDDFT" despite its frequency-domain formulation. This form of TDDFT is the mostly widely-used quantum-chemical method for excited states, due to a favorable combination of low cost and reasonable accuracy. The chapter surveys the accuracy of linear-response TDDFT, which is generally more sensitive to the details of the exchange-correlation functional as compared to ground-state DFT, and also describes some known systemic problems exhibited by this approach. Some of those problems can be corrected on a case-by-case basis using orbital-optimized, excited-state self-consistent field (SCF) calculations, in what is known as excited-state Kohn-Sham theory or a "∆SCF" procedure, a class of methods that includes restricted open-shell Kohn-Sham theory. Recent successes of these approaches are highlighted, including double excitations and core-level excitations. Finally, explicitly time-dependent (or "real-time") TDDFT involves propagation of the molecular orbitals in time following an external perturbation, according to the Kohn-Sham analogue of the time-dependent Schrödinger equation. The time-dependent approach has been used to model strong-field electron dynamics, and in the weak-field limit it provides a route to broadband spectra based on the time evolution of the dipole moment function. This is useful for describing high-energy excitations (as in x-ray spectroscopy) and in systems where the density of states is high, as demonstrated by a few examples.

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Section: Description Of Charge Transfermentioning

confidence: 99%

Density Functional Theory for Electronic Excited States

Herbert¹

2022

Preprint

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“…With a collection of around 98,000 vials of synthetic dyes, direct injection ESI‐Q‐TOF‐MS was used to differentiate the structure of colors by their molecular weights. The Weaver dye library could also be used to compare every vial with the known toxicants to see if there is any relation, helping with the chemical risk assessment, environmental impacts (Kuenemann et al, 2017), computationally predicting their spectroscopic properties (Marshburn et al, 2021), and structure‐toxicity relationships of these dyes (Umbuzeiro et al, 2019).…”

Section: Dye Ionization Methodology and Behaviormentioning

confidence: 99%

Synthetic dyes: A mass spectrometry approach and applications

Millbern

Trettin

et al. 2022

Mass Spectrometry Reviews

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Synthetic dyes are found in a wide variety of applications today, including but not limited to textiles, foods, and medicine. The analysis of these molecules is pertinent to several fields such as forensics, environmental monitoring, and quality control, all of which require the sensitivity and selectivity of analysis provided by mass spectrometry (MS). Recently, there has been an increase in the implementation of MS evaluation of synthetic dyes by various methods, with the majority of research thus far falling under electrospray ionization and moving toward direct ionization methods. This review covers an overview of the chemistry of synthetic dyes needed for the understanding of MS sample preparation and spectral results, current fields of application, ionization methods, and fragmentation trends and works that have been reported in recent years.

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Density-functional theory for electronic excited states

Herbert¹

2023

Theoretical and Computational Photochemistry

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Are all charge-transfer parameters created equally? A study of functional dependence and excited-state charge-transfer quantification across two dye families

Abstract: Small molecule organic dyes have many potential uses in medicine, textiles, forensics, and light-harvesting technology. Being able to computationally predict the spectroscopic properties of these dyes could greatly expedite screening...

Cited by 4 publications

References 59 publications

Density Functional Theory for Electronic Excited States

Density Functional Theory for Electronic Excited States

Synthetic dyes: A mass spectrometry approach and applications

Density-functional theory for electronic excited states

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