Excimer Energies

Zhao, Ruoqi; Hettich, Christian; Zhang, Jun; Liu, Meiyi; Gao, Jiali

doi:10.1021/acs.jpclett.3c00545

Cited by 10 publications

(17 citation statements)

References 92 publications

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“…An energy correlation diagram for the excimer complex of pentacene dimer can be found in reference. 5 As other polyaromatic acenes, anthracene has two closelying excited singlet states termed as the L a (S 1 ) and L b (S 2 ) states. The dimeric excimer of anthracene molecules was optimized to a symmetric geometry using TDDFT with M06-2X/cc-pVDZ, whereas the two monomers in the fishbone configuration in the crystal structure are not fully equivalent.…”

Section: Intimate Excimersmentioning

confidence: 99%

“…Electronic coupling among local states in these systems can be used to determine the rate of excited-state energy transfer. Unfortunately, little attention has been paid to energy decomposition analysis of intermolecular interactions in excited states, ,− although several studies of energy components of excited states have been reported. , Moreover, it is not always clear if the intuitive terms for the ground state can be adapted to molecular systems in the excited states. In this Perspective , we present a multistate energy decomposition analysis (MS-EDA) introduced in a recent preliminary report to define the energy terms relevant to intermolecular interactions in excited states.…”

Section: Introductionmentioning

confidence: 99%

“…Unfortunately, little attention has been paid to energy decomposition analysis of intermolecular interactions in excited states, ,− although several studies of energy components of excited states have been reported. , Moreover, it is not always clear if the intuitive terms for the ground state can be adapted to molecular systems in the excited states. In this Perspective , we present a multistate energy decomposition analysis (MS-EDA) introduced in a recent preliminary report to define the energy terms relevant to intermolecular interactions in excited states. This is now possible following the development of multistate density functional theory (MSDFT) to treat the ground state, excited states and diabatic states on an equal footing with the inclusion of electron correlation. − …”

Section: Introductionmentioning

confidence: 99%

“…Yet, there is an interest in defining intermediate diabatic states which can be used to represent excitations localized on individual monomers to understand the reaction rates of excited-state energy transfer and excitation induced oxidation–reduction reactions . Recently, we introduced a multistate approach, making use of multistate density functional theory (MSDFT), to define variationally optimizable intermediate states to interpret properties associated with excited-state processes, , including local excitation, exciton resonance, superexchange, and orbital-and-configuration delocalization. This Perspective further expands that work in several fronts.…”

Section: Introductionmentioning

confidence: 99%

“…In this Perspective, we present a multistate energy decomposition analysis (MS-EDA) introduced in a recent preliminary report 5 to define the energy terms relevant to intermolecular interactions in excited states. This is now possible following the development of multistate density functional theory (MSDFT) to treat the ground state, excited states and diabatic states on an equal footing with the inclusion of electron correlation.…”

Section: Introductionmentioning

confidence: 99%

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Multistate Energy Decomposition Analysis of Molecular Excited States

Hettich,

Zhang,

Kemper

et al. 2023

JACS Au

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A multistate energy decomposition analysis (MS-EDA) method is described to dissect the energy components in molecular complexes in excited states. In MS-EDA, the total binding energy of an excimer or an exciplex is partitioned into a ground-state term, called local interaction energy, and excited-state contributions that include exciton excitation energy, superexchange stabilization, and orbital and configuration-state delocalization. An important feature of MS-EDA is that key intermediate states associated with different energy terms can be variationally optimized, providing quantitative insights into widely used physical concepts such as exciton delocalization and superexchange charge-transfer effects in excited states. By introducing structure-weighted adiabatic excitation energy as the minimum photoexcitation energy needed to produce an excited-state complex, the binding energy of an exciplex and excimer can be defined. On the basis of the nature of intermolecular forces through MS-EDA analysis, it was found that molecular complexes in the excited states can be classified into three main categories, including (1) encounter excited-state complex, (2) charge-transfer exciplex, and (3) intimate excimer or exciplex. The illustrative examples in this Perspective highlight the interplay of local excitation polarization, exciton resonance, and superexchange effects in molecular excited states. It is hoped that MS-EDA can be a useful tool for understanding photochemical and photobiological processes.

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Section: Intimate Excimersmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Multistate Energy Decomposition Analysis of Molecular Excited States

Hettich,

Zhang,

Kemper

et al. 2023

JACS Au

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Nonorthogonal Multireference Wave Function Description of Triplet–Triplet Energy Transfer Couplings

Thompson,

Kempfer-Robertson,

Saha

et al. 2023

J. Chem. Theory Comput.

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In this study, the use of self-consistent field quasi-diabats is investigated for calculation of triplet energy transfer diabatic coupling elements. It is proposed that self-consistent field quasi-diabats are particularly useful for studying energy transfer (EnT) processes because orbital relaxation in response to changes in electron configuration is implicitly built into the model. The conceptual model that is developed allows for the simultaneous evaluation of direct and charge-transfer mechanisms to establish the importance of the different possible EnT mechanisms. The method’s performance is evaluated using two model systems: the ethylene dimer and ethylene with the methaniminium cation. While states that mediate the charge-transfer mechanism were found to be higher in energy than the states involved in the direct mechanism, the coupling elements that control the kinetics were found to be significantly larger in the charge-transfer mechanism. Subsequently, we discuss the advantage of the approach in the context of practical difficulties with the use of established approaches.

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Structure of Multi-State Correlation in Electronic Systems

Lu,

Gao

2024

J. Chem. Theory Comput.

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Beyond the Hohenberg−Kohn density functional theory for the ground state, it has been established that the Hamiltonian matrix for a finite number (N) of lowest eigenstates is a matrix density functional. Its fundamental variable�the matrix density D(r)�can be represented by, or mapped to, a set of auxiliary, multiconfigurational wave functions expressed as a linear combination of no more than N 2 determinant configurations. The latter defines a minimal active space (MAS), which naturally leads to the introduction of the correlation matrix functional, responsible for the electronic correlation effects outside the MAS. In this study, we report a set of rigorous conditions in the Hamiltonian matrix functional, derived by enforcing the symmetry of a Hilbert subspace, namely the subspace invariance property. We further establish a fundamental theorem on the correlation matrix functional. That is, given the correlation functional for a single state in the N-dimensional subspace, all elements of the correlation matrix functional for the entire subspace are uniquely determined. These findings reveal the intricate structure of electronic correlation within the Hilbert subspace of lowest eigenstates and suggest a promising direction for efficient simulation of excited states.

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Excimer Energies

Cited by 10 publications

References 92 publications

Multistate Energy Decomposition Analysis of Molecular Excited States

Multistate Energy Decomposition Analysis of Molecular Excited States

Nonorthogonal Multireference Wave Function Description of Triplet–Triplet Energy Transfer Couplings

Structure of Multi-State Correlation in Electronic Systems

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