Excited-state methods for molecular systems: Performance, pitfalls, and practical guidance DOI Open Access
Zachary J. Knepp, Gil M. Repa, Lisa A. Fredin

et al.

Chemical Physics Reviews, Journal Year: 2025, Volume and Issue: 6(2)

Published: May 1, 2025

Proper theoretical descriptions of ground and excited states are critical for understanding molecular photophysics photochemistry. Complex interactions in experimentally interesting systems require multiple approximations the underlying quantum mechanics to practically solve various physical observables. While high-level calculations small provide very accurate excitation energies, this accuracy does not always extend larger or other properties. Because this, “best” method study new molecules is clear, leading many researchers default inexpensive easy-to-use black-box methods. Unfortunately, even when these methods reproduce experimental it necessarily right reasons. Without physics, becomes challenging understand classes molecules. Consequently, predicted properties their trends may offer reliable mechanistic understanding. This review targeted at beginners computational chemistry who interested studying excited-state A brief overview common ground- covered easy reference during comparison The primary focus compare several important chromophores. performance each explored practitioners a road map on what work well different identify further that needs be done field.

Language: Английский

Shining Fresh Light on Complex Photoredox Mechanisms through Isolation of Intermediate Radical Anions DOI Creative Commons
Samuel J. Horsewill, Gabriele Hierlmeier,

Zahra Farasat

et al.

ACS Catalysis, Journal Year: 2023, Volume and Issue: 13(14), P. 9392 - 9403

Published: June 30, 2023

Photoredox catalysis (PRC) has gained enormous and wide-ranging interest in recent years but also been subject to significant mechanistic uncertainty, even controversy. To provide a method by which the missing understanding can begin be filled in, we demonstrate herein that it is possible isolate as authentic materials one-electron reduction products of representative PRC catalysts (PCs). Specifically, KC8 both 9,10-dicyanoanthracene naphthalene monoamide derivative presence cryptand provides convenient access corresponding [K(crypt)+][PC·-] salts clean fully characterized techniques including EPR XRD. Because PC·- states are key intermediates reactions, such isolation allows for highly controlled study these anions' specific reactivity hence their roles. As demonstration this principle, show used conveniently interrogate mechanisms recent, high-profile "conPET" "e-PRC" currently acute Using very simple experiments, able striking insights into reactions' underlying observe surprising levels hidden complexity would otherwise have challenging identify emphasize care control needed when interrogating interpreting mechanisms. These studies foundation far broader range questions around conPET, e-PRC, other reaction future, using same strategy isolation.

Language: Английский

Citations

34
Recent Progress in C–S Bond Formation via Electron Donor-Acceptor Photoactivation DOI
Sichang Wang, Liting Wang, Jin Cui

et al.

Organic & Biomolecular Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

This review summarizes recent progress in EDA complex-promoted C–S bond formation using various sulfur-containing substrates under mild conditions via visible light irradiation.

Language: Английский

Citations

0
Excited-state methods for molecular systems: Performance, pitfalls, and practical guidance DOI Open Access
Zachary J. Knepp, Gil M. Repa, Lisa A. Fredin

et al.

Chemical Physics Reviews, Journal Year: 2025, Volume and Issue: 6(2)

Published: May 1, 2025

Proper theoretical descriptions of ground and excited states are critical for understanding molecular photophysics photochemistry. Complex interactions in experimentally interesting systems require multiple approximations the underlying quantum mechanics to practically solve various physical observables. While high-level calculations small provide very accurate excitation energies, this accuracy does not always extend larger or other properties. Because this, “best” method study new molecules is clear, leading many researchers default inexpensive easy-to-use black-box methods. Unfortunately, even when these methods reproduce experimental it necessarily right reasons. Without physics, becomes challenging understand classes molecules. Consequently, predicted properties their trends may offer reliable mechanistic understanding. This review targeted at beginners computational chemistry who interested studying excited-state A brief overview common ground- covered easy reference during comparison The primary focus compare several important chromophores. performance each explored practitioners a road map on what work well different identify further that needs be done field.

Language: Английский

Citations

0