Vibronic exciton theory of singlet fission. II. Two-dimensional spectroscopic detection of the correlated triplet pair state

Tempelaar, Roel; Reichman, David R.

doi:10.1063/1.4982359

Cited by 56 publications

(56 citation statements)

References 62 publications

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“…Tempelaar and Reichman further improved their model by including vibrational excitations in the ground electronic state and expanding the ME space to include a triplet pair with one T 1 and one T n >1 excited state . The authors used this full model to simulate the two‐dimensional electronic spectroscopy (2DES) of crystalline pentacene, the first experiment that gave direct detection of the tt ‐type state .…”

Section: Exploration For Singlet Fission Mechanisms Through Dynamics mentioning

confidence: 99%

Theoretical Studies of Singlet Fission: Searching for Materials and Exploring Mechanisms

2018

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In this Review article, a survey is given for theoretical studies in the subject of singlet fission. Singlet fission converts one singlet exciton to two triplet excitons. With the doubled number of excitons and the longer lifetime of the triplets, singlet fission provides an avenue to improve the photoelectric conversion efficiency in organic photovoltaic devices. It has been a subject of intense research in the past decade. Theoretical studies play an essential role in understanding singlet fission. This article presents a Review of theoretical studies in singlet fission since 2006, the year when the research interest in this subject was reignited. Both electronic structure and dynamics studies are covered. Electronic structure studies provide guidelines for designing singlet fission chromophores and insights into the couplings between single‐ and multi‐excitonic states. The latter provides fundamental knowledge for engineering interchromophore conformations to enhance the fission efficiency. Dynamics studies reveal the importance of vibronic couplings in singlet fission.

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Section: Exploration For Singlet Fission Mechanisms Through Dynamics mentioning

confidence: 99%

Theoretical Studies of Singlet Fission: Searching for Materials and Exploring Mechanisms

2018

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“…This state was found to consist of triplet pair states dressed by a single vibration, and labeled TT * 1 . In the second paper, hereafter Paper II, 18 the vibronic, microscopic model was held to an additional stringent test by comparing simulations with measurements 8 of two-dimensional electronic spectra (2DES). A satisfactory agreement confirmed the credibility to the model, and opened the opportunity to analyze the optical transitions associated with the triplet pair state, in particular those involving higher-lying triplet excitons, TT n (n > 1).…”

Section: Introductionmentioning

confidence: 99%

Vibronic exciton theory of singlet fission. III. How vibronic coupling and thermodynamics promote rapid triplet generation in pentacene crystals

Tempelaar

Reichman

2018

The Journal of Chemical Physics

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109

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We extend the vibronic exciton theory introduced in our previous work to study singlet fission dynamics, in particular addressing recent indications of the importance of vibronic coupling in this process. A microscopic and non-perturbative treatment of electronic and selected vibrational degrees of freedom in combination with Redfield theory allows us to dynamically consider clusters of molecules under conditions close to those in molecular crystals that exhibit fission. Using bulk pentacene as a concrete example, our results identify a number of factors that render fission rapid and effective. Strong coupling to high-frequency Holstein modes generates resonances between the photo-prepared singlet and product triplet states. We furthermore find the large number of triplet combinations associated with bulk periodic systems to be critical to the fission process under such vibronically resonant conditions. In addition, we present results including, in an approximate manner, the effects of Peierls coupling, indicating that this factor can both enhance and suppress fission depending on its interplay with vibronic resonance and thermodynamics.

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“…Some emphasize the need for an intermediate dark delocalized "charge-transfer" excitation [3,11,20,21,24]; others highlight the importance of nuclear zero-point and thermal motion in facilitating the fission process [25][26][27]. Berkelbach et al [28] and more recently Tempelaar et al [29] incorporated both the crystal environment and symmetry, as well as lattice vibration effects, into an approach that can explain recent reports of SF dynamics, with input from ab initio many-body perturbation theory (MBPT) calculations. Very recently, Kryjevski et al [30] used a MBPT approach to evaluate SF rate in carbon nanotubes with periodic boundary conditions.…”

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Origins of Singlet Fission in Solid Pentacene from an ab initio Green’s Function Approach

et al. 2017

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We develop a new first-principles approach to predict and understand rates of singlet fission with an ab initio Green's-function formalism based on many-body perturbation theory. Starting with singlet and triplet excitons computed from a GW plus Bethe-Salpeter equation approach, we calculate the exciton-biexciton coupling to lowest order in the Coulomb interaction, assuming a final state consisting of two noninteracting spin-correlated triplets with finite center-of-mass momentum. For crystalline pentacene, symmetries dictate that the only purely Coulombic fission decay process from a bright singlet state requires a final state consisting of two inequivalent nearly degenerate triplets of nonzero, equal and opposite, center-of-mass momenta. For such a process, we predict a singlet lifetime of 30-70 fs, in very good agreement with experimental data, indicating that this process can dominate singlet fission in crystalline pentacene. Our approach is general and provides a framework for predicting and understanding multiexciton interactions in solids.

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Vibronic exciton theory of singlet fission. II. Two-dimensional spectroscopic detection of the correlated triplet pair state

Cited by 56 publications

References 62 publications

Theoretical Studies of Singlet Fission: Searching for Materials and Exploring Mechanisms

Theoretical Studies of Singlet Fission: Searching for Materials and Exploring Mechanisms

Vibronic exciton theory of singlet fission. III. How vibronic coupling and thermodynamics promote rapid triplet generation in pentacene crystals

Origins of Singlet Fission in Solid Pentacene from an ab initio Green’s Function Approach

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