Electronic Couplings for Singlet Fission Processes Based on The Fragment Particle-Hole Densities DOI Creative Commons
Yu‐Chen Wang,

Shishi Feng,

Yi Kong

et al.

Published: April 25, 2023

A new diabatization scheme is proposed to calculate the electronic couplings for singlet fission process in multichromophoric systems. In this approach, a robust descriptor that treats single and multiple excitations on an equal footing adopted quantify localization degree of particle hole densities states. By maximally localizing particles holes terms predefined molecular fragments, quasi-diabatic states with well-defined characters (locally excited, charge transfer, correlated triplet pair, etc.) can be automatically constructed as linear combinations adiabatic ones, directly obtained. This approach very general it applies various spin multiplicities combined kinds preliminary structure calculations. Due high numerical efficiency, able manipulate more than 100 diabatization. The applications tetracene dimer trimer reveals high-lying multiply-excited transfer have significant influences both formation separation even enlarge coupling latter by one order magnitude.

Language: Английский

The Role of Double Excitations in Exciton Dynamics of Multiazobenzenes: Trisazobenzenophane as a Test Case DOI Creative Commons
Evgenii Titov

Published: May 30, 2024

Molecular exciton dynamics underlie energy and charge transfer processes in organic multichromophoric systems. A particularly interesting class of the latter are multiphotochromic systems made molecules capable photochemical transformations. Exciton assemblies photoswitches have been recently investigated using either molecular model or supermolecular configuration interaction (CI) singles, both approaches being based on a semiempirical Hamiltonian combined with surface hopping dynamics. Here, we study how inclusion double excitations nonadiabatic simulations affect multiazobenzenes, trisazobenzenophane as an example. We find that CI singles doubles yield virtually same timescale dynamical localization, ∼50 fs for studied multiazobenzene. However, considerably affects excited state lifetimes isomerization quantum yields.

Language: Английский

Citations

0
The Role of Double Excitations in Exciton Dynamics of Multiazobenzenes: Trisazobenzenophane as a Test Case DOI Creative Commons
Evgenii Titov

The Journal of Physical Chemistry Letters, Journal Year: 2024, Volume and Issue: 15(29), P. 7482 - 7488

Published: July 16, 2024

Molecular exciton dynamics underlie energy and charge transfer processes in organic multichromophoric systems. A particularly interesting class of the latter is multiphotochromic systems made molecules capable photochemical transformations. Exciton assemblies photoswitches have been recently investigated using either molecular model or supermolecular configuration interaction (CI) singles, both approaches being based on a semiempirical Hamiltonian combined with surface hopping dynamics. Here, we study how inclusion double excitations nonadiabatic simulations affects multiazobenzenes, trisazobenzenophane as an example. We find that CI singles doubles yield virtually same time scale dynamical localization, ∼50 fs for studied multiazobenzene. However, considerably excited state lifetimes isomerization quantum yields.

Language: Английский

Citations

0
Elektronendynamiksimulation mit Wellenfunktionen für Materialanwendungen/Trendbericht Theoretische Chemie 2024 (1/3) DOI Open Access
Annika Bande

Nachrichten aus der Chemie, Journal Year: 2024, Volume and Issue: 72(11), P. 48 - 52

Published: Oct. 31, 2024

Abstract Zeitabhängige Simulationen der Elektronendynamik gewinnen für optische Materialien und lichtinduzierte Photoreaktionen an Gewicht. Verständliche visuelle Ergebnisdarstellungen moderne effiziente Rechenverfahren helfen dabei, die Technik zu verbreiten. Renaissance Semiempirik: In jüngerer Zeit tragen semiempirische Methoden wieder vermehrt dazu bei, Vorhersagekraft quantenchemischer steigern. Dichtefunktionaltheorie: Auf Suche nach einem universellen Austauschkorrelationsfunktional sind mathematisch flexible Ansätze Hybridfunktionale besonders vielversprechend, etwa lokale oder mit lokaler Reichweitenseparierung.

Citations

0
Temperature-Dependent Spin-Driven Dimerization Determines the Ultrafast Dynamics of a Copper(II)-Bound Tripyrrindione Radical DOI Creative Commons
Anshu Kumar,

Benjamin Thompson,

Ritika Gautam

et al.

Published: Sept. 29, 2023

Radicals and other open-shell molecules play a central role in chemical transformations redox chemistry. While radicals are often highly reactive, stable radical systems desirable for range of potential applications ranging from materials chemistry catalysis to spintronics quantum information. Here we investigate the ultrafast properties system with temperature-dependent spin-tunable properties. This complex, Cu(II) hexaethyl tripyrrin-1,14-dione, accommodates unpaired electrons localized on both copper metal center tripyrrolic ligand. Two-dimensional electronic spectroscopy measurements tripyrrin-1,14-dione were collected at room temperature 77 K. At temperature, present as monomers have short, picosecond lifetimes. K, dimer form mediated by ferromagnetic anti-ferromagnetic coupling. reversible spin-driven dimerization changes optical system, generating long-lived excitonic states.

Language: Английский

Citations

1
Electronic Couplings for Singlet Fission Processes Based on The Fragment Particle-Hole Densities DOI Creative Commons
Yu‐Chen Wang,

Shishi Feng,

Yi Kong

et al.

Published: April 25, 2023

A new diabatization scheme is proposed to calculate the electronic couplings for singlet fission process in multichromophoric systems. In this approach, a robust descriptor that treats single and multiple excitations on an equal footing adopted quantify localization degree of particle hole densities states. By maximally localizing particles holes terms predefined molecular fragments, quasi-diabatic states with well-defined characters (locally excited, charge transfer, correlated triplet pair, etc.) can be automatically constructed as linear combinations adiabatic ones, directly obtained. This approach very general it applies various spin multiplicities combined kinds preliminary structure calculations. Due high numerical efficiency, able manipulate more than 100 diabatization. The applications tetracene dimer trimer reveals high-lying multiply-excited transfer have significant influences both formation separation even enlarge coupling latter by one order magnitude.

Language: Английский

Citations

0