: We present a novel three-layer approach based on multilevel density functional theory (MLDFT) and polarizable molecular mechanics to simulate the electronic excitations of chemical systems embedded in an external environment within the time-dependent DFT formalism. In our method, the electronic structure of a target system, the chromophore, is determined in the field of an embedded inactive layer, which is treated as frozen. Long-range interactions are described by employing the polarizable fluctuating charge (FQ) force field. The resulting MLDFT/FQ thus accurately describes both electrostatics (and polarization) and non-electrostatic target-environment interactions. The robustness and reliability of the approach are demonstrated by comparing our results with experimental data reported for various organic molecules in solution.

Time-Dependent Multilevel Density Functional Theory

Giovannini, Tommaso
;
2024

Abstract

: We present a novel three-layer approach based on multilevel density functional theory (MLDFT) and polarizable molecular mechanics to simulate the electronic excitations of chemical systems embedded in an external environment within the time-dependent DFT formalism. In our method, the electronic structure of a target system, the chromophore, is determined in the field of an embedded inactive layer, which is treated as frozen. Long-range interactions are described by employing the polarizable fluctuating charge (FQ) force field. The resulting MLDFT/FQ thus accurately describes both electrostatics (and polarization) and non-electrostatic target-environment interactions. The robustness and reliability of the approach are demonstrated by comparing our results with experimental data reported for various organic molecules in solution.
2024
Settore CHIM/02 - Chimica Fisica
Settore FIS/03 - Fisica della Materia
Settore CHEM-02/A - Chimica fisica
Settore PHYS-04/A - Fisica teorica della materia, modelli, metodi matematici e applicazioni
Charge force-fields; linear-response; embedding theory; hartree-fock; fragmentation; energies; potentials; transition; solvation; mechanics
   Coupled cluster theory for polaritons: changing molecular properties with quantum light
   QuantumLight
   European Commission
   Horizon 2020 Framework Programme
   101020016
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11384/147323
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