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 screening and dissociation of excitons at finite temperatures from first principles.

The properties of excitons, or correlated electron-hole pairs, are of paramount importance to optoelectronic applications of materials. A central component of exciton physics is the electron-hole interaction, which is commonly treated as screened solely by electrons within a material. However, nuclear motion can screen this Coulomb interaction as well, with several recent studies developing model approaches for approximating the phonon screening of excitonic properties. While these model approaches tend to improve agreement with experiment, they rely on several approximations that restrict their applicability to a wide range of materials, and thus far they have neglected the effect of finite temperatures. Here, we develop a fully first-principles, parameter-free approach to compute the temperature-dependent effects of phonon screening within the ab initio [Formula: see text]-Bethe-Salpeter equation framework. We recover previously proposed models of phonon screening as well-defined limits of our general framework, and discuss their validity by comparing them against our first-principles results. We develop an efficient computational workflow and apply it to a diverse set of semiconductors, specifically AlN, CdS, GaN, MgO, and [Formula: see text]. We demonstrate under different physical scenarios how excitons may be screened by multiple polar optical or acoustic phonons, how their binding energies can exhibit strong temperature dependence, and the ultrafast timescales on which they dissociate into free electron-hole pairs.

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.