Singlet fission is a photoconversion process that generates a doubly excited, maximally spin entangled pair state. This state has applications to quantum information and computing that are only beginning to be realized. In this article, we construct and analyze a spin-exciton hamiltonian to describe the dynamics of the two-triplet state. We find the selection rules that connect the doubly excited, spin-singlet state to the manifold of quintet states and comment on the mechanism and conditions for the transition into formally independent triplets. For adjacent dimers that are oriented and immobilized in an inert host, singlet fission can be strongly state-selective. We make predictions for electron paramagnetic resonance experiments and re-assign some transitions from recent literature. Our results give conditions for which magnetic resonance pulses can drive transitions between optically polarized magnetic sublevels of the two-exciton states, making it possible to realize quantum gates at room temperature in these systems.
Singlet fission is a process whereby two triplet excitons can be produced from one photon, potentially increasing the efficiency of photovoltaic devices. Endothermic singlet fission is desired for maximum energy conversion efficiency, and such systems have been shown to form an excimer-like state with multi-excitonic character prior to the appearance of triplets. However, the role of the excimer as an intermediate has, until now, been unclear. Here we show, using 5,12-bis((triisopropylsilyl)ethynyl)tetracene in solution as a prototypical example, that, rather than acting as an intermediate, th…
Internal conversion from the photoexcited state to a correlated singlet triplet-pair state is believed to be the precursor of singlet fission in carotenoids. We present numerical simulations of this process using a pi-electron model that fully accounts for electron-electron interactions and electron-nuclear coupling. The time-evolution of the electrons is determined rigorously using the time-dependent density matrix renormalization method, while the nuclei are evolved via the Ehrenfest equations of motion. We apply this to zeaxanthin, a carotenoid chain with 22 conjugated carbon atoms (i.e., 1…
Polaritons are unique hybrid light-matter states that offer an alternative way to manipulate chemical processes and change material properties. In this work we theoretically demonstrate that singlet fission dynamics can be accelerated under strong light-matter coupling. For superexchange-mediated singlet fission, state mixing speeds up the dynamics in cavities when the lower polariton is close in energy to the multiexcitonic triplet-pair state. We show that this effect is more pronounced in non-conventional singlet fission materials in which the energy gap between the bright singlet exciton an…
Singlet fission (SF) is a potential pathway for significant enhancement of efficiency in organic solar cells (OSC). In this paper, we study singlet fission in a pair of polyene molecules in two different stacking arrangements employing exact many-body wave packet dynamics. In the non-interacting model, the SF yield is absent. The individual molecules are treated within Hubbard and Pariser-Parr-Pople (PPP) models and the interaction between them involves transfer terms, intersite electron repulsions and site-charge--bond-charge repulsion terms. Initial wave packet is constructed from excited si…
Singlet fission, a process that splits a singlet exciton into a biexciton, has promise in quantum information. We report time-resolved electron paramagnetic resonance measurements on a molecule, TIPS-BP1$'$, designed to exhibit strongly state-selective relaxation to specific magnetic spin sublevels. The resulting optically pumped "spin polarization" is a nearly pure initial state from the ensemble. The long-lived spin coherences modulate the signal intrinsically, allowing a new measurement scheme that substantially removes noise and uncertainty in the magnetic resonance spectra. A nonadiabatic…
Singlet fission, a spin-allowed energy transfer process generating two triplet excitons from one singlet exciton, has the potential to dramatically increase the efficiency of organic solar cells. However, the dynamical mechanism of this phenomenon is not fully understood and a complete, microscopic theory of singlet fission is lacking. In this work, we assemble the components of a comprehensive microscopic theory of singlet fission that connects excited state quantum chemistry calculations with finite-temperature quantum relaxation theory. We elaborate on the distinction between localized diab…
Intramolecular singlet fission (iSF) materials provide remarkable advantages in terms of tunable electronic structures, and quantum chemistry studies have indicated strong electronic coupling modulation by high frequency phonon modes. In this work, we formulate a microscopic model of iSF with simultaneous diagonal and off-diagonal coupling to high-frequency modes. A non-perturbative treatment, the Dirac-Frenkel time-dependent variational approach is adopted using the multiple Davydov trial states. It is shown that both diagonal and off-diagonal coupling can aid efficient singlet fission if exc…
In the preceding paper, we assembled the theoretical components necessary for a unified framework of singlet fission, a type of multiexciton generation producing two triplet excitons from one singlet exciton. In this paper, we apply our methodology to molecular dimers of pentacene, a widely studied material that exhibits singlet fission. We address a longstanding theoretical issue, namely whether singlet fission proceeds via two sequential electron transfer steps mediated by a charge-transfer state or via a direct two-electron transfer process. We find evidence for a superexchange mediated mec…
The mechanisms underlying coherent and thermally activated singlet exciton fission in pi-stacked acene crystals are clarified based on quantum dynamics simulations parameterized against a highly correlated description of the electronic excitations and their couplings to intramolecular and intermolecular vibrations. In TIPS-pentacene crystals, the relative longitudinal shift of the molecular backbones yields large electronic couplings of the triplet exciton pair with both the singlet exciton and charge transfer (CT) states. CT-mediated superexchange and direct pathways are found to contribute s…
Singlet exciton fission (SF), the conversion of one spin-singlet exciton (S1) into two spin-triplet excitons (T1), could provide a means to overcome the Shockley-Queisser limit in photovoltaics. SF as measured by the decay of S1 has been shown to occur efficiently and independently of temperature even when the energy of S1 is as much as 200 meV less than 2T1. Here, we study films of TIPS-tetracene using transient optical spectroscopy and show that the initial rise of the triplet pair state (TT) occurs in 300 fs, matched by rapid loss of S1 stimulated emission, and that this process is mediated…
Singlet fission is a spin-allowed exciton multiplication process in organic semiconductors that converts one spin-singlet exciton to two triplet excitons. It offers the potential to enhance solar energy conversion by circumventing the Shockley-Queisser limit on efficiency. Recently, the mechanism of the primary singlet fission process in pentacene and its derivatives have been extensively investigated, however, the nature of the primary ultrafast process in singlet fission is still a matter of debate. Here, we study the singlet fission process in a pentacene film by employing a combination of …
Several recent electron spin resonance studies have observed a quintet multiexciton state during the singlet fission process. Here we provide a general theoretical explanation for the generation of this state by invoking a time-varying exchange coupling between pairs of triplet excitons, and subsequently solving the relevant time-varying spin Hamiltonian for a range of transition times. We simulate experimental ESR spectra and draw qualitative conclusions about the adiabatic/diabatic transition between triplet pair spin states.
Singlet fission is commonly defined to involve a process by which an overall singlet state with local triplet structure spin-decoheres into two triplet states, thereby completing the fission process. This process, often defined in loose terms involving the multiplicity of the overall state, is investigated here using a uniform Heisenberg spin-chain subject to a dephasing environmental interaction. We introduce new results from quantum information theory which enables the quantification of coherence and entanglement in a bi- and multipartite system. The calculated measures of these quantum effe…
Singlet fission, the molecular process through which photons are effectively converted into pairs of lower energy triplet excitons, holds promise as a means of boosting photovoltaic device efficiencies. In the preceding article of this series, we formulated a vibronic theory of singlet fission, inspired by previous experimental and theoretical studies suggesting that vibronic coupling plays an important role in fission dynamics. Here, we extend our model in order to simulate two-dimensional electronic spectra, through which the theory is further validated based on a comparison to recent measur…
When considering the optimal molecular packing to realize charge multiplication in organic photovoltaic materials, subtle changes in intermolecular charge transfer (CT) coupling can strongly modulate singlet fission. To understand why certain packing morphologies are more conducive to charge multiplication by triplet pair (TT) formation, we measure the diffraction-limited transient absorption (TA) response from four single-crystal functionalized derivatives of fluorinated anthradithiophene: diF R-ADT (R = TES, TSBS, TDMS, TBDMS). diF TES-ADT and diF TDMS-ADT both exhibit 2D brickwork packing s…
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…
We report quadruple configuration interaction calculations within the extended Pariser$-$Parr$-$Pople Hamiltonian on the excited states of aggregates of polyenes, crystalline acenes, and covalently linked dimers of acene molecules. We determine the precise energy orderings and analyze the cluster wave functions in order to arrive at a comprehensive physical understanding of singlet fission in these diverse families of materials. Our computational approach allows us to retain a very large number of basis states and thereby obtain the correct relative energy orderings of one electron$-$one hole …
Recent time-resolved spectroscopic experiments have indicated that vibronic coupling plays a vital role in facilitating the process of singlet fission. In this work, which forms the first article of a series, we set out to unravel the mechanisms underlying singlet fission through a vibronic exciton theory. We formulate a model in which both electronic and vibrational degrees of freedom are treated microscopically and non-perturbatively. Using pentacene as a prototypical material for singlet fission, we subject our theory to comparison with measurements on polarization-resolved absorption of si…
Experimental investigations of magnetic field dependent kinetics of singlet fission (SF)processes in some organic semiconductors [i.e. splitting of excited singlet (S_1) state into a triplet exciton pair] have revealed the important specific feature of obtained kinetic curves, associated with decaying intensities I(t) of fluorescence from S_1-state. Kinetic curves, measured in different magnetic fields, are found to cross each other. We show that this kinetic curves crossing (KCC) effect is a general feature of geminate condensed phase reactions, resulting from simple characteristic properties…
Short coherence times present a primary obstacle in quantum computing and sensing applications. In atomic systems, clock transitions (CTs), formed from avoided crossings in an applied Zeeman field, can substantially increase coherence times. We show how CTs can dampen intrinsic and extrinsic sources of quantum noise in molecules. Conical intersections between two periodic potentials form CTs in electron paramagnetic resonance experiments of the spin-polarized singlet fission photoproduct. We report on a pair of CTs for a two-chromophore molecule in terms of the Zeeman field strength, molecular…
Spin-entaglement has been proposed and extensively used in the case of correlated triplet pairs which are intermediate states in singlet fission process in select organic semiconductors. Here, we employ quantum process tomography of polarization entangled photon-pairs resonant with the excited state absorption of these states to investigate the nature of the inherent quantum correlations and to explore for an unambiguous proof for the existence of exciton entanglement.
Experiments in several intramolecular singlet fission materials have indicated that the triplet-triplet spin biexciton has a much longer lifetime than believed until recently, opening up loss mechanisms that can annihilate the biexciton prior to its dissociation to free triplets. We have performed many-body calculations of excited state wavefunctions of hypothetical phenylene-linked anthracene molecules to better understand linker-dependent behavior of dimers of larger acenes being investigated as potential singlet fission candidates. The calculations reveal unanticipated features that we show…
Kinetics of singlet fission in organic semiconductors, in which the excited singlet state (S_1) spontaneously splits into a pair of triplet (T) excitons, is known to be strongly influenced by back geminate annihilation of TT-pairs. We show that this influence can be properly described only by taking into account the diffusive exciton migration. The migration effect is treated in the model of two kinetically coupled states: the intermediate state of interacting TT-pairs and the state of migrating excitons. Within this model the singlet fission (including magnetic field effects) is studied as ap…
Probing extended polyene systems with energy in excess of the bright state ($1^1B_u^+$/$S_2$) band edge generates triplets via singlet fission. This process is not thought to involve the $2^1A_g^-$/$S_1$ state, suggesting that other states play a role. Using density matrix renormalisation group (DMRG) calculations of the Pariser-Parr-Pople-Peierls Hamiltonian, we investigate candidate states that could be involved in singlet fission. We find that the relaxed $1^1B_u^-$, and $3^1A_g^-$ singlet states and $1^5A_g^-$ quintet state lie below the $S_2$ state. The $1^1B_u^-$, $3^1A_g^-$ and $1^5A_g^…
Singlet fission (SF) can potentially break the Shockley-Queisser efficiency limit in single-junction solar cells by splitting one photo-excited singlet exciton (S1) into two triplets (2T1) in organic semiconductors. A dark multi-exciton (ME) state has been proposed as the intermediate connecting S1 to 2T1. However, the exact nature of this ME state, especially how the doubly-excited triplets interact, remains elusive. Here, we report a quantitative study on the magnetic dipolar interaction between SF-induced correlated triplets in tetracene crystals by monitoring quantum beats relevant to the …
In the third generation photovoltaic device, the main physical mechanism that the photoelectric conversion efficiency is enhanced is the singlet fission (SF). In order to accurately describe the SF and reveal physical process in theoretically, we introduce the anomalous process (AP) in SF dynamics based on previous model, including anomalous fission, anomalous fusion, anomalous dissociation and combination of triplet pair states, anomalous decay and diffusion of single triplet exciton. The effects of the AP on SF are investigated by the kinetic model with time-dependent coefficient. Further, a…
Singlet exciton fission (SEF) is a key process in the development of efficient opto-electronic devices. An aspect that is rarely probed directly, and yet has a tremendous impact on SEF properties, is the nuclear structure and dynamics involved in this process. Here we directly observe the nuclear dynamics accompanying the SEF process in single crystal pentacene using femtosecond electron diffraction. The data reveal coherent atomic motions at 1 THz, incoherent motions, and an anisotropic lattice distortion representing the polaronic character of the triplet excitons. Combining molecular dynami…
Singlet fission is an important candidate to increase energy conversion efficiency in organic photovoltaics by providing a pathway to increase the quantum yield of excitons per photon absorbed in select materials. We investigate the dependence of exciton quantum yield for acenes in the strong light-matter interaction (polariton) regime, where the materials are embedded in optical microcavities. Starting from an open-quantum-systems approach, we build a kinetic model for time-evolution of species of interest in the presence of quenchers and show that polaritons can decrease or increase exciton …
Recent advances in singlet-fission research make it imperative that structure-property correlations that determine optical signatures of the triplet-triplet spin biexciton as well as its binding energy be understood precisely. We report many-body calculations of excited state absorptions from the triplet exciton and the triplet-triplet biexciton from two transversally linked dimers of pentacene derivatives. Comparison of experiment against theory leads to new interpretations of experiments performed earlier. We show that in the para-linked isomer the triplet-triplet does not dissociate to free…
The photo-driven process of singlet fission generates coupled triplet pairs (TT) with fundamentally intriguing and potentially useful properties. The quintet 5TT0 sublevel is particularly interesting for quantum information because it is highly entangled, addressable with microwave pulses, and could be detected using optical techniques. Previous theoretical work on a model Hamiltonian and nonadiabatic transition theory, called the JDE model, has determined that this sublevel can be selectively populated if certain conditions are met. Among the most challenging, the molecules within the dimer u…
We describe our dynamical simulations of the excited states of the carotenoid, neurosporene, following its photoexcitation into the 'bright' (nominally $1^1B_u^+$) state. We employ the adaptive tDMRG method on the UV model of $π$-conjugated electrons and use the Ehrenfest equations of motion to simulate the coupled nuclei dynamics. To account for the experimental and theoretical uncertainty in the relative energetic ordering of the nominal $1^1B_u^+$ and $2^1A_g^-$ states at the Franck-Condon point, we consider two parameter sets. In both cases there is ultrafast internal conversion from the '…
We develop a powerful tree tensor network states method that is capable of simulating exciton-phonon quantum dynamics of larger molecular complexes and open quantum systems with multiple bosonic environments. We interface this method with ab initio density functional theory to study singlet exciton fission (SF) in a pentacene dimer. With access to the full vibronic many-body wave function, we track and assign the contributions of different symmetry classes of vibrations to SF and derive energy surfaces, enabling us to dissect, understand, and describe the strongly coupled electronic and vibrat…
Carrier multiplication by singlet exciton fission enhances photovoltaic conversion efficiencies in organic solids. This decay of one singlet exciton into two triplet states promises to overcome the Shockley-Queisser limit as up to two electrons may be harvested per absorbed photon. Intermolecular coupling is deemed mandatory for both, singlet exciton fission and a band-like transport. Such a coupling is manifested, $e.g.$, by the Davydov-splitting of the lowest-energy exciton transition in crystalline organic solids. For the model system perfluoropentacene, the corresponding transitions in the…
Structurally well-defined TIPS-acetylene substituted tetracene (TIPS BT1') and pentacene (TIPS BP1') dimers utilizing a [2.2.1] bicyclic norbornyl bridge have been studied -primarily using time-resolved spectroscopic methods - to uncover mechanistic details about primary steps in singlet fission leading to formation of the biexcitonic 1TT state as well as decay pathways to the ground state. For TIPS BP1' in room temperature toluene, 1TT formation is rapid and complete, occurring in 4.4 ps. Decay to the ground state in 100 ns is the primary loss pathway for 1TT in this system. For TIPS BT1', th…
