Influence of Electronic Correlations on Electron-Phonon Interactions of Molecular Systems with the GW and Coupled Cluster Methods.

Electron-phonon interactions are of great importance to a variety of physical phenomena, and their accurate description is an important goal for first-principles calculations. Isolated examples of materials and molecular systems have emerged where electron-phonon coupling is enhanced over density functional theory (DFT) when using the Green's-function-based ab initio GW method, which provides a more accurate description of electronic correlations. It is, however, unclear how general this enhancement is and how employing high-end quantum chemistry methods, which further improve the description of electronic correlations, might further alter electron-phonon interactions over GW or DFT. Here, we address these questions by computing the renormalization of the highest occupied molecular orbital energies of Thiel's set of organic molecules by harmonic vibrations using DFT, GW, and equation-of-motion coupled-cluster calculations. We find that, depending on the amount of exact exchange included in the DFT starting point, GW can increase the magnitude of the electron-phonon coupling across Thiel's set of molecules by an average factor of 1.1-1.8 compared to the underlying DFT, while equation-of-motion coupled-cluster leads to an increase of 1.4-2. The electron-phonon coupling predicted with the ab initio GW method is generally in much closer agreement to coupled cluster values compared to DFT, establishing GW as a promising route for accurately computing electron-phonon phenomena in molecules and beyond at a much lower computational cost than higher-end quantum chemistry techniques.

Decoupling excitons from high-frequency vibrations in organic molecules.

The coupling of excitons in π-conjugated molecules to high-frequency vibrational modes, particularly carbon-carbon stretch modes (1,000-1,600 cm-1) has been thought to be unavoidable1,2. These high-frequency modes accelerate non-radiative losses and limit the performance of light-emitting diodes, fluorescent biomarkers and photovoltaic devices. Here, by combining broadband impulsive vibrational spectroscopy, first-principles modelling and synthetic chemistry, we explore exciton-vibration coupling in a range of π-conjugated molecules. We uncover two design rules that decouple excitons from high-frequency vibrations. First, when the exciton wavefunction has a substantial charge-transfer character with spatially disjoint electron and hole densities, we find that high-frequency modes can be localized to either the donor or acceptor moiety, so that they do not significantly perturb the exciton energy or its spatial distribution. Second, it is possible to select materials such that the participating molecular orbitals have a symmetry-imposed non-bonding character and are, thus, decoupled from the high-frequency vibrational modes that modulate the π-bond order. We exemplify both these design rules by creating a series of spin radical systems that have very efficient near-infrared emission (680-800 nm) from charge-transfer excitons. We show that these systems have substantial coupling to vibrational modes only below 250 cm-1, frequencies that are too low to allow fast non-radiative decay. This enables non-radiative decay rates to be suppressed by nearly two orders of magnitude in comparison to π-conjugated molecules with similar bandgaps. Our results show that losses due to coupling to high-frequency modes need not be a fundamental property of these systems.

Phonon-Induced Localization of Excitons in Molecular Crystals from First Principles.

The spatial extent of excitons in molecular systems underpins their photophysics and utility for optoelectronic applications. Phonons are reported to lead to both exciton localization and delocalization. However, a microscopic understanding of phonon-induced (de)localization is lacking, in particular, how localized states form, the role of specific vibrations, and the relative importance of quantum and thermal nuclear fluctuations. Here, we present a first-principles study of these phenomena in solid pentacene, a prototypical molecular crystal, capturing the formation of bound excitons, exciton-phonon coupling to all orders, and phonon anharmonicity, using density functional theory, the ab initio GW-Bethe-Salpeter equation approach, finite-difference, and path integral techniques. We find that for pentacene zero-point nuclear motion causes uniformly strong localization, with thermal motion providing additional localization only for Wannier-Mott-like excitons. Anharmonic effects drive temperature-dependent localization, and, while such effects prevent the emergence of highly delocalized excitons, we explore the conditions under which these might be realized.

Dielectric control of reverse intersystem crossing in thermally activated delayed fluorescence emitters.

Thermally activated delayed fluorescence enables organic semiconductors with charge transfer-type excitons to convert dark triplet states into bright singlets via reverse intersystem crossing. However, thus far, the contribution from the dielectric environment has received insufficient attention. Here we study the role of the dielectric environment in a range of thermally activated delayed fluorescence materials with varying changes in dipole moment upon optical excitation. In dipolar emitters, we observe how environmental reorganization after excitation triggers the full charge transfer exciton formation, minimizing the singlet-triplet energy gap, with the emergence of two (reactant-inactive) modes acting as a vibrational fingerprint of the charge transfer product. In contrast, the dielectric environment plays a smaller role in less dipolar materials. The analysis of energy-time trajectories and their free-energy functions reveals that the dielectric environment substantially reduces the activation energy for reverse intersystem crossing in dipolar thermally activated delayed fluorescence emitters, increasing the reverse intersystem crossing rate by three orders of magnitude versus the isolated molecule.

Cyclo[18]carbon including zero-point motion: ground state, first singlet and triplet excitations, and hole transfer.

Recent synthesis of cyclo[18]carbon has spurred increasing interest in carbon rings. We focus on a comparative inspection of ground and excited states, as well as of hole transfer properties of cumulenic and polyynic cyclo[18]carbon via Density Functional Theory (DFT), time-dependent DFT (TD-DFT) and real-time time-dependent DFT (RT-TDDFT). Zero-point vibrations are also accounted for, using a Monte Carlo sampling technique and a less exact, yet mode-resolved, quadratic approximation. The inclusion of zero-point vibrations leads to a red-shift on the HOMO-LUMO gap and the first singlet and triplet excitation energies of both conformations, correcting the values of the 'static' configurations by 9% to 24%. Next, we oxidize the molecule, creating a hole at one carbon atom. Hole transfer along polyynic cyclo[18]carbon is decreased in magnitude compared to its cumulenic counterpart and lacks the symmetric features the latter displays. Contributions by each mode to energy changes and hole transfer between diametrically opposed atoms vary, with specific bond-stretching modes being dominant.

Microcavity-like exciton-polaritons can be the primary photoexcitation in bare organic semiconductors.

Strong-coupling between excitons and confined photonic modes can lead to the formation of new quasi-particles termed exciton-polaritons which can display a range of interesting properties such as super-fluidity, ultrafast transport and Bose-Einstein condensation. Strong-coupling typically occurs when an excitonic material is confided in a dielectric or plasmonic microcavity. Here, we show polaritons can form at room temperature in a range of chemically diverse, organic semiconductor thin films, despite the absence of an external cavity. We find evidence of strong light-matter coupling via angle-dependent peak splittings in the reflectivity spectra of the materials and emission from collective polariton states. We additionally show exciton-polaritons are the primary photoexcitation in these organic materials by directly imaging their ultrafast (5 × 106 m s-1), ultralong (~270 nm) transport. These results open-up new fundamental physics and could enable a new generation of organic optoelectronic and light harvesting devices based on cavity-free exciton-polaritons.

Systematic improvement of molecular excited state calculations by inclusion of nuclear quantum motion: A mode-resolved picture and the effect of molecular size.

The energies of molecular excited states arise as solutions to the electronic Schrödinger equation and are often compared to experiment. At the same time, nuclear quantum motion is known to be important and to induce a redshift of excited state energies. However, it is thus far unclear whether incorporating nuclear quantum motion in molecular excited state calculations leads to a systematic improvement of their predictive accuracy, making further investigation necessary. Here, we present such an investigation by employing two first-principles methods for capturing the effect of quantum fluctuations on excited state energies, which we apply to the Thiel set of organic molecules. We show that accounting for zero-point motion leads to much improved agreement with experiment, compared to "static" calculations that only account for electronic effects, and the magnitude of the redshift can become as large as 1.36 eV. Moreover, we show that the effect of nuclear quantum motion on excited state energies largely depends on the molecular size, with smaller molecules exhibiting larger redshifts. Our methodology also makes it possible to analyze the contribution of individual vibrational normal modes to the redshift of excited state energies, and in several molecules, we identify a limited number of modes dominating this effect. Overall, our study provides a foundation for systematically quantifying the shift of excited state energies due to nuclear quantum motion and for understanding this effect at a microscopic level.

Exciton Diffusion in Highly-Ordered One Dimensional Conjugated Polymers: Effects of Back-Bone Torsion, Electronic Symmetry, Phonons and Annihilation.

Many optoelectronic devices based on organic materials require rapid and long-range singlet exciton transport. Key factors controlling exciton transport include material structure, exciton-phonon coupling and electronic state symmetry. Here, we employ femtosecond transient absorption microscopy to study the influence of these parameters on exciton transport in one-dimensional conjugated polymers. We find that excitons with 21Ag- symmetry and a planar backbone exhibit a significantly higher diffusion coefficient (34 ± 10 cm2 s-1) compared to excitons with 11Bu+ symmetry (7 ± 6 cm2 s-1) with a twisted backbone. We also find that exciton transport in the 21Ag- state occurs without exciton-exciton annihilation. Both 21Ag- and 11Bu+ states are found to exhibit subdiffusive behavior. Ab initio GW-BSE calculations reveal that this is due to the comparable strengths of the exciton-phonon interaction and exciton coupling. Our results demonstrate the link between electronic state symmetry, backbone torsion and phonons in exciton transport in π-conjugated polymers.

First principles modeling of exciton-polaritons in polydiacetylene chains.

Exciton-polaritons in organic materials are hybrid states that result from the strong interaction of photons and the bound excitons that these materials host. Organic polaritons hold great interest for optoelectronic applications; however, progress toward this end has been impeded by the lack of a first principles approach that quantifies light-matter interactions in these systems, which would allow the formulation of molecular design rules. Here, we present a theoretical framework that combines first principles calculations for excitons with classical electrodynamics in order to quantify light-matter interactions. We exemplify our approach by studying variants of the conjugated polymer polydiacetylene, and we show that a large polymer conjugation length is critical toward strong exciton-photon coupling, hence underlying the importance of pure structures without static disorder. By comparing to our experimental reflectivity measurements, we show that the coupling of excitons to vibrations, manifested by phonon side bands in the absorption, has a strong impact on the magnitude of light-matter coupling over a range of frequencies. Our approach opens the way toward a deeper understanding of polaritons in organic materials, and we highlight that a quantitatively accurate calculation of the exciton-photon interaction would require accounting for all sources of disorder self-consistently.

Thiol-Anchored TIPS-Tetracene Ligands with Quantitative Triplet Energy Transfer to PbS Quantum Dots and Improved Thermal Stability.

Triplet energy transfer between inorganic quantum dots (QDs) and organic materials plays a fundamental role in many optoelectronic applications based on these nanocomposites. Attaching organic molecules to the QD as transmitter ligands has been shown to facilitate transfer both to and from QDs. Here we show that the often disregarded thiol anchoring group can achieve quantitative triplet energy transfer yields in a PbS QD system with 6,11-bis[(triisopropylsilyl)ethynyl]tetracene-2-methylthiol (TET-SH) ligands. We demonstrate efficient triplet transfer in a singlet fission-based photon multiplication system with 5,12-bis[(triisopropylsilyl)ethynyl]tetracene generating triplets in solution that transfer to the PbS QDs via the thiol ligand TET-SH. Importantly, we demonstrate the increased thermal stability of the PbS/TET-SH system, compared to the traditional carboxylic acid counterpart, allowing for higher photoluminescence quantum yields.

Switching between Coherent and Incoherent Singlet Fission via Solvent-Induced Symmetry Breaking.

Singlet fission in organic semiconductors causes a singlet exciton to decay into a pair of triplet excitons and holds potential for increasing the efficiency of photovoltaic devices. In this combined experimental and theoretical study, we reveal that a covalent dimer of the organic semiconductor tetracene undergoes activated singlet fission by qualitatively different mechanisms depending on the solvent environment. We show that intramolecular vibrations are an integral part of this mechanism, giving rise to mixing between charge transfer and triplet pair excitations. Either coherent or incoherent singlet fission can occur, depending on the transient solvent-induced energetic proximity between the states, giving rise to complex variation of the singlet fission mechanism and time scale in the different environments. Our results suggest a more general principle for controlling the efficiency of photochemical reactions by utilizing transient interactions to tune the energetics of reactant and product states and switch between incoherent and coherent dynamics.

A molecular movie of ultrafast singlet fission.

The complex dynamics of ultrafast photoinduced reactions are governed by their evolution along vibronically coupled potential energy surfaces. It is now often possible to identify such processes, but a detailed depiction of the crucial nuclear degrees of freedom involved typically remains elusive. Here, combining excited-state time-domain Raman spectroscopy and tree-tensor network state simulations, we construct the full 108-atom molecular movie of ultrafast singlet fission in a pentacene dimer, explicitly treating 252 vibrational modes on 5 electronic states. We assign the tuning and coupling modes, quantifying their relative intensities and contributions, and demonstrate how these modes coherently synchronise to drive the reaction. Our combined experimental and theoretical approach reveals the atomic-scale singlet fission mechanism and can be generalized to other ultrafast photoinduced reactions in complex systems. This will enable mechanistic insight on a detailed structural level, with the ultimate aim to rationally design molecules to maximise the efficiency of photoinduced reactions.

Non-equilibrium relaxation of hot states in organic semiconductors: Impact of mode-selective excitation on charge transfer.

The theoretical study of open quantum systems strongly coupled to a vibrational environment remains computationally challenging due to the strongly non-Markovian characteristics of the dynamics. We study this problem in the case of a molecular dimer of the organic semiconductor tetracene, the exciton states of which are strongly coupled to a few hundreds of molecular vibrations. To do so, we employ a previously developed tensor network approach, based on the formalism of matrix product states. By analyzing the entanglement structure of the system wavefunction, we can expand it in a tree tensor network state, which allows us to perform a fully quantum mechanical time evolution of the exciton-vibrational system, including the effect of 156 molecular vibrations. We simulate the dynamics of hot states, i.e., states resulting from excess energy photoexcitation, by constructing various initial bath states, and show that the exciton system indeed has a memory of those initial configurations. In particular, the specific pathway of vibrational relaxation is shown to strongly affect the quantum coherence between exciton states in time scales relevant for the ultrafast dynamics of application-relevant processes such as charge transfer. The preferential excitation of low-frequency modes leads to a limited number of relaxation pathways, thus "protecting" quantum coherence and leading to a significant increase in the charge transfer yield in the dimer structure.