Intramolecular Charge Transfer and Local Excitation in Organic Fluorescent Photoredox Catalysts Explained by RASCI-PDFT

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Abstract

We investigate the electronically excited states of two recently synthesized organic fluorescent photoredox catalysts of the dihydrophenazine family. The mixed charge transfer and local excitation behavior of dark and bright transitions is unveiled by multiconfiguration pair-density functional theory (MC-PDFT) based on a restricted active space configuration interaction (RASCI) wave function (RASCI-PDFT). The RASCI-PDFT calculations give an accurate description of the experimental optical absorption spectra with active spaces too large for conventional complete active space self-consistent-field calculations. These results were achieved by the inclusion of many valence orbitals in the active space and their optimization within a cost-effective restricted active space self-consistent field framework without a RAS2 subspace, followed by calculations at the RASCI level including orbitals in RAS2. This novel strategy can be extended to systems that need a large number of orbitals in the active space.

Original languageEnglish (US)
Pages (from-to)12061-12070
Number of pages10
JournalJournal of Physical Chemistry C
Volume122
Issue number22
DOIs
StatePublished - Jun 7 2018

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configuration interaction
Charge transfer
charge transfer
catalysts
Catalysts
excitation
Wave functions
Excited states
Light absorption
Density functional theory
Absorption spectra
orbitals
self consistent fields
Costs
optical spectrum
optical absorption
wave functions
inclusions
density functional theory
costs

Cite this

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title = "Intramolecular Charge Transfer and Local Excitation in Organic Fluorescent Photoredox Catalysts Explained by RASCI-PDFT",
abstract = "We investigate the electronically excited states of two recently synthesized organic fluorescent photoredox catalysts of the dihydrophenazine family. The mixed charge transfer and local excitation behavior of dark and bright transitions is unveiled by multiconfiguration pair-density functional theory (MC-PDFT) based on a restricted active space configuration interaction (RASCI) wave function (RASCI-PDFT). The RASCI-PDFT calculations give an accurate description of the experimental optical absorption spectra with active spaces too large for conventional complete active space self-consistent-field calculations. These results were achieved by the inclusion of many valence orbitals in the active space and their optimization within a cost-effective restricted active space self-consistent field framework without a RAS2 subspace, followed by calculations at the RASCI level including orbitals in RAS2. This novel strategy can be extended to systems that need a large number of orbitals in the active space.",
author = "Davide Presti and Truhlar, {Donald G} and Laura Gagliardi",
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T1 - Intramolecular Charge Transfer and Local Excitation in Organic Fluorescent Photoredox Catalysts Explained by RASCI-PDFT

AU - Presti, Davide

AU - Truhlar, Donald G

AU - Gagliardi, Laura

PY - 2018/6/7

Y1 - 2018/6/7

N2 - We investigate the electronically excited states of two recently synthesized organic fluorescent photoredox catalysts of the dihydrophenazine family. The mixed charge transfer and local excitation behavior of dark and bright transitions is unveiled by multiconfiguration pair-density functional theory (MC-PDFT) based on a restricted active space configuration interaction (RASCI) wave function (RASCI-PDFT). The RASCI-PDFT calculations give an accurate description of the experimental optical absorption spectra with active spaces too large for conventional complete active space self-consistent-field calculations. These results were achieved by the inclusion of many valence orbitals in the active space and their optimization within a cost-effective restricted active space self-consistent field framework without a RAS2 subspace, followed by calculations at the RASCI level including orbitals in RAS2. This novel strategy can be extended to systems that need a large number of orbitals in the active space.

AB - We investigate the electronically excited states of two recently synthesized organic fluorescent photoredox catalysts of the dihydrophenazine family. The mixed charge transfer and local excitation behavior of dark and bright transitions is unveiled by multiconfiguration pair-density functional theory (MC-PDFT) based on a restricted active space configuration interaction (RASCI) wave function (RASCI-PDFT). The RASCI-PDFT calculations give an accurate description of the experimental optical absorption spectra with active spaces too large for conventional complete active space self-consistent-field calculations. These results were achieved by the inclusion of many valence orbitals in the active space and their optimization within a cost-effective restricted active space self-consistent field framework without a RAS2 subspace, followed by calculations at the RASCI level including orbitals in RAS2. This novel strategy can be extended to systems that need a large number of orbitals in the active space.

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