Singlet fission, a multistep molecular process in which one photon generates two triplet excitons, holds great technological promise. Here, by applying a combination of transient transmittance and ...two-dimensional electronic spectroscopy with 5 fs laser pulses, we resolve the full set of fission steps before the onset of spin dephasing. In addition to its role as a viable singlet fission material, single-crystalline rubrene is selected because its energetics and transition dipole alignment uniquely allow for the unambiguous identification of the various fission steps through their contributions to distinct spectroscopic features. The measurements reveal that the neighboring correlated triplet pair achieves its maximum population within 20 fs. Subsequent growth of the triplet signal on picosecond time scales is attributable to spatial separation of the triplets, proceeding nonadiabatically through weakly coupled but near-resonant states. As such, we provide evidence in crystalline rubrene for a singlet fission step that, until now, has not been convincingly observed.
The thermodynamic entropy of coarse-grained (CG) models stands as one of the most important properties for quantifying the missing information during the CG process and for establishing transferable ...(or extendible) CG interactions. However, performing additional CG simulations on top of model construction often leads to significant additional computational overhead. In this work, we propose a simple hierarchical framework for predicting the thermodynamic entropies of various molecular CG systems. Our approach employs a decomposition of the CG interactions, enabling the estimation of the CG partition function and thermodynamic properties a priori. Starting from the ideal gas description, we leverage classical perturbation theory to systematically incorporate simple yet essential interactions, ranging from the hard sphere model to the generalized van der Waals model. Additionally, we propose an alternative approach based on multiparticle correlation functions, allowing for systematic improvements through higher-order correlations. Numerical applications to molecular liquids validate the high fidelity of our approach, and our computational protocols demonstrate that a reduced model with simple energetics can reasonably estimate the thermodynamic entropy of CG models without performing any CG simulations. Overall, our findings present a systematic framework for estimating not only the entropy but also other thermodynamic properties of CG models, relying solely on information from the reference system.
Lead-halide perovskites have emerged as promising materials for photovoltaic and optoelectronic applications. Their significantly anharmonic lattice motion, in contrast to conventional harmonic ...semiconductors, presents a conceptual challenge in understanding the genesis of their exceptional optoelectronic properties. Here we report a strongly temperature dependent luminescence Stokes shift in the electronic spectra of both hybrid and inorganic lead-bromide perovskite single crystals. This behavior stands in stark contrast to that exhibited by more conventional crystalline semiconductors. We correlate the electronic spectra with the anti-Stokes and Stokes Raman vibrational spectra. Dielectric solvation theories, originally developed for excited molecules dissolved in polar liquids, reproduce our experimental observations. Our approach, which invokes a classical Debye-like relaxation process, captures the dielectric response originating from the incipient anharmonicity of the LO phonon at about 20 meV (160 cm
) in the lead-bromide framework. We reconcile this liquid-like model incorporating thermally-activated dielectric solvation with more standard solid-state theories of the emission Stokes shift in crystalline semiconductors.
Determining the Fourier representation of various molecular interactions is important for constructing density-based field theories from a microscopic point of view, enabling a multiscale bridge ...between microscopic and mesoscopic descriptions. However, due to the strongly repulsive nature of short-ranged interactions, interparticle interactions cannot be formally defined in Fourier space, which renders coarse-grained (CG) approaches in k-space somewhat ambiguous. In this paper, we address this issue by designing a perturbative expansion of pair interactions in reciprocal space. Our perturbation theory, starting from reciprocal space, elucidates the microscopic origins underlying zeroth-order (long-range attractions) and divergent repulsive interactions from higher order contributions. We propose a systematic framework for constructing a faithful Fourier-space representation of molecular interactions, capturing key structural correlations in various systems, including simple model systems and molecular CG models of liquids. Building upon the Ornstein–Zernike equation, our approach can be combined with appropriate closure relations, and to further improve the closure approximations, we develop a bottom-up parameterization strategy for inferring the bridge function from microscopic statistics. By incorporating the bridge function into the Fourier representation, our findings suggest a systematic, bottom-up approach to performing coarse-graining in reciprocal space, leading to the systematic construction of a bottom-up classical field theory of complex aqueous systems.
Abstract
The non-equilibrium dynamics of matter excited by light may produce electronic phases, such as laser-induced high-transition-temperature superconductivity, that do not exist in equilibrium. ...Here we simulate the dynamics of a metal driven at initial time by a spatially uniform pump that excites dipole-active vibrational modes which couple nonlinearly to electrons. We provide evidence for rapid loss of spatial coherence, leading to emergent effective disorder in the dynamics, which arises in a system unitarily evolving under a translation-invariant Hamiltonian, and dominates the electronic behavior as the system evolves towards a correlated electron-phonon long-time state, possibly explaining why transient superconductivity is not observed. Our framework provides a basis within which to understand correlation dynamics in current pump-probe experiments of vibrationally coupled electrons, highlight the importance of the evolution of phase coherence, and demonstrate that pumped electron-phonon systems provide a means of realizing dynamically induced disorder in translation-invariant systems.
We have identified excited exciton states in monolayers of MoS2 and WS2 supported on fused silica by means of photoluminescence excitation spectroscopy. In monolayer WS2, the positions of the excited ...A exciton states imply an exciton binding energy of 0.32 eV. In monolayer MoS2, excited exciton transitions are observed at energies of 2.24 and 2.34 eV. Assigning these states to the B exciton Rydberg series yields an exciton binding energy of 0.44 eV.
Recent experiments have suggested that ground-state chemical kinetics can be suppressed or enhanced by coupling molecular vibrations with a cavity radiation mode. Here, we develop an analytical rate ...theory for cavity-modified chemical kinetics based on the Pollak–Grabert–Hänggi theory. Unlike previous work, our theory covers the complete range of solvent friction values, from the energy-diffusion-limited to the spatial-diffusion-limited regimes. We show that chemical kinetics is enhanced when bath friction is weak and suppressed when bath friction is strong. For weak bath friction, the resonant photon frequency (at which the maximum modification of the chemical rate is achieved) is close to the reactant well. In the strong friction limit, the resonant photon frequency is instead close to the barrier frequency. Finally, we observe that rate changes as a function of the photon frequency are much sharper and more sizable in the weak friction limit than in the strong friction limit.
In monolayer graphene, substitutional doping during growth can be used to alter its electronic properties. We used scanning tunneling microscopy, Raman spectroscopy, x-ray spectroscopy, and first ...principles calculations to characterize individual nitrogen dopants in monolayer graphene grown on a copper substrate. Individual nitrogen atoms were incorporated as graphitic dopants, and a fraction of the extra electron on each nitrogen atom was delocalized into the graphene lattice. The electronic structure of nitrogen-doped graphene was strongly modified only within a few lattice spacings of the site of the nitrogen dopant. These findings show that chemical doping is a promising route to achieving high-quality graphene films with a large carrier concentration.
We discuss the linear and two-photon spectroscopic selection rules for spin-singlet excitons in monolayer transition-metal dichalcogenides. Our microscopic formalism combines a fully k-dependent ...few-orbital band structure with a many-body Bethe-Salpeter equation treatment of the electron-hole interaction, using a model dielectric function. We show analytically and numerically that the single-particle, valley-dependent selection rules are preserved in the presence of excitonic effects. Furthermore, we definitively demonstrate that the bright (one-photon allowed) excitons have s-type azimuthal symmetry and that dark p-type excitons can be probed via two-photon spectroscopy. The screened Coulomb interaction in these materials substantially deviates from the 1/ epsilon sub(0)r form; this breaks the "accidental" angular momentum degeneracy in the exciton spectrum, such that the exciton has a lower energy than the exciton by at least 50 meV. We compare our calculated two-photon absorption spectra to recent experimental measurements.
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