Accessing the triplet state of perylenediimide by radical-enhanced intersystem crossing

Mayländer, Maximilian; Nolden, Oliver; Franz, Michael; Chen, Su; Bancroft, Laura; Qiu, Yunfan; Wasielewski, Michael R.; Gilch, Peter; Richert, Sabine

doi:10.1039/d2sc01899c

Cited by 27 publications

(46 citation statements)

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“…In this series, perylene is covalently bound to seven different radicals, which are commonly used in experimental studies on molecular three-spin systems. [45][46][47][48][49][50][51][52][53][54] The goal was to determine the influence of the nature of the radical on the magnitude of the exchange interaction(s) and to verify whether systematic trends can be identified. Fig.…”

Section: Choice Of the Molecules And Methodsmentioning

confidence: 99%

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Calculation of exchange couplings in the electronically excited state of molecular three-spin systems

2022

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Section: Choice Of the Molecules And Methodsmentioning

confidence: 99%

“…In this series, perylene is covalently bound to seven different radicals, which are commonly used in experimental studies on molecular three-spin systems. 45–54…”

Section: Theorymentioning

confidence: 99%

Calculation of exchange couplings in the electronically excited state of molecular three-spin systems

2022

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“…Management of the spin state in spintronic materials can be useful to affect display efficiency of organic light-emitting diodes, among other applications. , For example, an aromatic compound such as benzene and pyridine can be directly excited to the triplet state in the presence of a free radical species such as oxygen and NO, , whereas the triplet state of closed-shell porphyrins can become highly luminescent with an unpaired metal d-electron . In a recent biomolecular application of the spintronic coupling between 9,10-anthraquinone and a stable nitroxide radical (Figure A), it was found that its spin state can be controlled by visible light through DNA binding.…”

Section: Illustrative Examplesmentioning

confidence: 99%

Minimal Active Space: NOSCF and NOSI in Multistate Density Functional Theory

Zhao

Zhang

et al. 2022

J. Chem. Theory Comput.

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In this Perspective, we introduce a minimal active space (MAS) for the lowest N eigenstates of a molecular system in the framework of multistate density functional theory (MSDFT), consisting of no more than N 2 nonorthgonal Slater determinants. In comparison with some methods in wave function theory in which one seeks to expand the ever increasing size of an active space to approximate the wave functions, it is possible to have an upper bound in MSDFT because the auxiliary states in a MAS are used to represent the exact Ndimensional matrix density function D(r). Here, we partition the total Hamiltonian matrix functional [ ] D into an orbital-dependent part, including multistate kinetic energy T ms and Coulomb-exchange energy E Hx plus an external potential energy ∫ dr v(r)D(r), and a correlation matrix density functional [ ] D c . The latter accounts for the part of correlation energy not explicitly included in the minimal active space. A major difference from Kohn−Sham DFT is that state interactions are necessary to represent the N-matrix density D(r) in MSDFT, rather than a noninteracting reference state for the scalar ground-state density ρ o (r). Two computational approaches are highlighted. We first derive a set of nonorthogonal multistate self-consistent-field (NOSCF) equations for the variational optimization of [ ] D . We introduce the multistate correlation potential, as the functional derivative of [ ] D c, which includes both correlation effects within the MAS and that from the correlation matrix functional. Alternatively, we describe a nonorthogonal state interaction (NOSI) procedure, in which the determinant functions are optimized separately. Both computational methods are useful for determining the exact eigenstate energies and for constructing variational diabatic states, provided that the universal correlation matrix functional is known. It is hoped that this discussion would stimulate developments of approximate multistate density functionals both for the ground and excited states.

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“…Management of spin state in spintronic materials can be useful to affect display efficiency of organic light-emitting diode, among other applications. 63,64 For example, an aromatic compound such as benzene and pyridine can be directly excited to the triplet state in the presence of a free radical species such as oxygen and NO, 65,66 whereas the triplet state of closed-shell porphyrins can become highly luminescent with an unpaired metal d-electron. 67 In a recent biomolecular application of the spintronic coupling between 9,10anthraquinone and a stable nitroxide radical (Figure 2A), 68 it was found that its spin state can be controlled by visible light through DNA binding.…”

Section: Spin Coupling Of Anthraquinone and Nitroxide Free Radicalmentioning

confidence: 99%

Minimal Active Space: NOSCF and NOSI in Multistate Density Functional Theory

Zhao

Zhang

et al. 2022

Preprint

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In this Perspective, we introduce a minimal active space (MAS) for the lowest N eigenstates of a molecular system in the framework of a multistate density functional theory (MSDFT), consisting of no more than N2 nonorthgonal Slater determinants. In comparison with some methods in wave function theory in which one seeks to expand the ever increasing size of an active space to approximate the wave functions, it is possible to have an upper bound in MSDFT because the auxiliary states in a MAS are used to represent the exact N-dimensional matrix density D(r). In analogy to Kohn-Sham DFT, we partition the total Hamiltonian matrix functional H[D] into an orbital-dependent part, including multistate kinetic energy Tms and Coulomb exchange energy EHx plus an external potential energy R dr v(r)D(r), and a correlation matrix density functional Ec[D]. The latter accounts for the part of correlation energy not explicitly included in the minimal active space. However, a major difference from Kohn-Sham DFT is that state interactions are necessary to represent the N-matrix density D(r) in MSDFT, rather than a non-interacting reference state for the scalar ground-state density ρo(r). Two computational approaches are highlighted. We first derive a set of non-orthogonal multistate self-consistent-field (NOSCF) equations for the variational optimization of H[D]. We introduce the multistate correlation potential, as the functional derivative of Ec[D], which includes both correlation effects within the MAS and that from the correlation matrix functional. Alternatively, we describe a non-orthogonal state interaction (NOSI) procedure, in which the determinant functions are optimized separately. Both computational methods are useful for determining the exact eigenstate energies and for constructing variational diabatic states, provided that the universal correlation matrix functional is known. It is hoped that this discussion would stimulate developments of approximate multistate density functionals both for the ground and excited states.

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Accessing the triplet state of perylenediimide by radical-enhanced intersystem crossing

Abstract: Owing to their exceptional photophysical properties and high photostability, perylene diimide (PDI) chromophores have found various applications as building blocks of materials for organic electronics. In many light-induced processes in...

Cited by 27 publications

References 87 publications

Calculation of exchange couplings in the electronically excited state of molecular three-spin systems

Calculation of exchange couplings in the electronically excited state of molecular three-spin systems

Minimal Active Space: NOSCF and NOSI in Multistate Density Functional Theory

Minimal Active Space: NOSCF and NOSI in Multistate Density Functional Theory

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