Abstract Electron–phonon coupling is fundamental to condensed-matter physics, governing various physical phenomena and properties in both conventional and quantum materials. Here we propose and demonstrate two-dimensional electron–phonon coupling spectroscopy that can directly extract the electron–phonon coupling matrix elements for specific phonon modes and different electron energies. Using this technique, we measure the electron energy dependence of the electron–phonon coupling strength for individual phonon modes. It allows us to identify distinct signatures distinguishing non-local Su–Schrieffer–Heeger-type couplings from local Holstein-type couplings. Applying this methodology to a methylammonium lead iodide perovskite, we reveal particularly different properties, for example, temperature dependence or anisotropy, of the electron–phonon couplings of two pronounced phonon modes. Our approach provides insights into the microscopic origin of the electron–phonon coupling and has potential applications in phonon-mediated ultrafast control material properties.

Phonon dynamics are a critical factor to control the optical properties of excited states in light-emitting materials. Here, we report an extremely slow relaxation of photoexcited lattice vibrations enabled by assembling the donor-acceptor (D-A) molecules [2-(9,9-dimethylacridin-10(9H)-yl)-9,9-dimethyl-9H-thioxanthene 10,10-dioxide], namely AC molecules, into dipolar crystal. By using photoexcitation-modulated Raman spectroscopy, we find that the crystalline-lattice vibrations monitored by Raman-scattering laser beam of 785 nm demonstrate an un-usual slow relaxation in the time scale of seconds after ceasing photoexcitation beam of 343 nm in such dipolar crystal. This presents extremely slow phonon dynamics enabled by crystalline-assembling the D-A molecules into a dipolar crystal. Simultaneously, the photoluminescence (PL) exhibits a prolonged behavior, lasting 10 ms after ceasing photoexcitation in dipolar AC crystal. This phenomenon provides an experimental hypothesis that the slow phonon dynamics function as an important mechanism to unusually prolong excited states dynamics upon crystalline-assembling the D-A molecules into dipolar crystal. This hypothesis can be verified by directly suppressing the phonon dynamics through freezing D-A molecular liquid into dipolar crystalline solid at 77 K to largely prolong the PL to 1 s- after removing photoexcitation. Clearly, crystalline-assembling D-A molecules provide the necessary conditions to enable slow phonon dynamics toward prolonging excited states dynamics.

Abstract Electron–phonon coupling is fundamental to condensed-matter physics, governing various physical phenomena and properties in both conventional and quantum materials. Here we propose and demonstrate two-dimensional electron–phonon coupling spectroscopy that can directly extract the electron–phonon coupling matrix elements for specific phonon modes and different electron energies. Using this technique, we measure the electron energy dependence of the electron–phonon coupling strength for individual phonon modes. It allows us to identify distinct signatures distinguishing non-local Su–Schrieffer–Heeger-type couplings from local Holstein-type couplings. Applying this methodology to a methylammonium lead iodide perovskite, we reveal particularly different properties, for example, temperature dependence or anisotropy, of the electron–phonon couplings of two pronounced phonon modes. Our approach provides insights into the microscopic origin of the electron–phonon coupling and has potential applications in phonon-mediated ultrafast control material properties.

Phonon dynamics are a critical factor to control the optical properties of excited states in light-emitting materials. Here, we report an extremely slow relaxation of photoexcited lattice vibrations enabled by assembling the donor-acceptor (D-A) molecules [2-(9,9-dimethylacridin-10(9H)-yl)-9,9-dimethyl-9H-thioxanthene 10,10-dioxide], namely AC molecules, into dipolar crystal. By using photoexcitation-modulated Raman spectroscopy, we find that the crystalline-lattice vibrations monitored by Raman-scattering laser beam of 785 nm demonstrate an un-usual slow relaxation in the time scale of seconds after ceasing photoexcitation beam of 343 nm in such dipolar crystal. This presents extremely slow phonon dynamics enabled by crystalline-assembling the D-A molecules into a dipolar crystal. Simultaneously, the photoluminescence (PL) exhibits a prolonged behavior, lasting 10 ms after ceasing photoexcitation in dipolar AC crystal. This phenomenon provides an experimental hypothesis that the slow phonon dynamics function as an important mechanism to unusually prolong excited states dynamics upon crystalline-assembling the D-A molecules into dipolar crystal. This hypothesis can be verified by directly suppressing the phonon dynamics through freezing D-A molecular liquid into dipolar crystalline solid at 77 K to largely prolong the PL to 1 s- after removing photoexcitation. Clearly, crystalline-assembling D-A molecules provide the necessary conditions to enable slow phonon dynamics toward prolonging excited states dynamics.

Optical cavities, resonant with vibrational or electronic transitions of material within the cavity, enable control of light-matter interaction. Previous studies have reported cavity-induced modifications of chemical reactivity, fluorescence, phase behavior, and charge transport. Here, we explore the effect of resonant cavity-phonon coupling on the transient photoconductivity in a hybrid organic-inorganic perovskite. To this end, we measure the ultrafast photoconductivity response of perovskite in a tunable Fabry-Pérot terahertz cavity, designed to be transparent for optical excitation. The terahertz-cavity field-phonon interaction causes apparent Rabi splitting between the perovskite phonon mode and the cavity mode. We explore whether the cavity-phonon interaction affects the material's electron-phonon interaction by determining the charge-carrier mobility through photoconductivity. Despite the apparent hybridization of cavity and phonon modes, we show that the perovskite properties in both ground (phonon response) and excited (photoconductive response) states remain unaffected by the tunable light-matter interaction. Yet the response of the integral perovskite-terahertz optical cavity system depends critically on the interaction strength of the cavity with the phonon: the transient terahertz response to optical excitation can be increased up to threefold by tuning the cavity-perovskite interaction strength. These results enable tunable switches and frequency-controlled induced transparency devices.

Electron-phonon interaction underlies the conventional and exotic electrodynamics. Moreover, specific phonon modes have emerged as an efficient channels to modulate band structures, transport, and topology on picosecond time scales and with high precision in atomic motions. Such an ultrafast phonon control could allow for achieving electronic states not accessible in static environments. However, the main physical quantity, the electron-phonon coupling (EPC) strength is highly theoretical in nature and has been measured via an averaged effect. In this talk, I will introduce the two-dimensional electron-phonon-coupling spectroscopy (2D EPC) that we have recently developed for directly extracting the EPC strength in a phonon mode- and electron energy-resolved manner. First, I will show our design principle of this new spectroscopy, quantum pathways that contribute to the observables, and how the EPC strength is quantified from the signal field. Then, the experimental realization, analysis protocol, and the proof of concept result on methylammonium lead iodide perovskite films will follow. Finally, I will discuss the potential of this 2D EPC spectroscopy in condensed matter physics.

Understanding carrier dynamics in photoexcited metal-halide perovskites is key for optoelectronic devices such as solar cells (low carrier densities) and lasers (high carrier densities). Trapping processes at low carrier densities and many-body recombination at high densities can significantly alter the dynamics of photoexcited carriers. Combining optical-pump/THz probe and transient absorption spectroscopy we examine carrier responses over a wide density range (10¹⁴-10¹⁹ cm^-3) and temperatures (78-315 K) in the prototypical methylammonium lead iodide perovskite. At densities below ∼10¹⁵ cm^-3 (room temperature, sunlight conditions), fast carrier trapping at shallow trap states occurs within a few picoseconds. As excited carrier densities increase, trapping saturates, and the carrier response stabilizes, lasting up to hundreds of picoseconds at densities around ∼10¹⁷ cm^-3. Above 10¹⁸ cm^-3 a Mott transition sets in overlapping polaron wave functions leading to ultrafast annihilation, tentatively assigned as an Auger recombination process, occurring over a few picoseconds. We map out trap-dominated, direct recombination-dominated, and Mott-dominated density regimes from 78 to 315 K, ultimately enabling the construction of an electronic "phase diagram". These findings clarify carrier behavior across operational conditions, aiding material optimization for optoelectronics operating in the low (e.g., photovoltaics) and high (e.g., laser) carrier density regimes.

Groundbreaking advances in materials and chemical research have been driven by the development of atomistic simulations. However, the broader applicability of atomistic simulations remains limited, as they inherently depend on energy models that are either approximate or computationally prohibitive for large-scale simulations. Machine learning interatomic potentials (MLIPs) have recently emerged as a promising class of energy models, but their deployment also remains challenging due to the scarcity of systematic protocols for generating training data spanning diverse structural regimes. Here we introduce GAIA, an end-to-end automated framework that streamlines dataset construction for the development of general-purpose reactive MLIPs. GAIA combines a metadynamics-based exploration scheme with closed-loop data expansion for the efficient sampling of a broad spectrum of atomic arrangements, thereby addressing the reliance on heuristics in conventional dataset generation. Using GAIA, we constructed Titan25, a benchmark-scale dataset, and trained an MLIP that closely matches both static and dynamic density functional theory results. The resulting model reproduces key experimental observations across distinct modes of reactivity, including detonation, coalescence, and catalytic processes. GAIA thus helps bridge the gap between simulation and experiment, paving the way toward scalable and general MLIPs capable of describing a wide range of materials and chemical processes.

Understanding carrier dynamics in photoexcited metal-halide perovskites is key for optoelectronic devices such as solar cells (low carrier densities) and lasers (high carrier densities). Trapping processes at low carrier densities and many-body recombination at high densities can significantly alter the dynamics of photoexcited carriers. Combining optical-pump/THz probe and transient absorption spectroscopy we examine carrier responses over a wide density range (10^14-10^19 cm-3) and temperatures (78-315K) in the prototypical methylammonium lead iodide perovskite. At densities below ~10^15 cm-3 (room temperature, sunlight conditions), fast carrier trapping at shallow trap states occurs within a few picoseconds. As excited carrier densities increase, trapping saturates, and the carrier response stabilizes, lasting up to hundreds of picoseconds at densities around ~10^17 cm-3. Above 10^18 cm-3 a Mott transition sets in: overlapping polaron wavefunctions lead to ultrafast annihilation through an Auger recombination process occurring over a few picoseconds. We map out trap-dominated, direct recombination-dominated, and Mott-dominated density regimes from 78-315 K, ultimately enabling the construction of an electronic phase diagram. These findings clarify carrier behavior across operational conditions, aiding material optimization for optoelectronics operating in the low (e.g. photovoltaics) and high (e.g. laser) carrier density regimes.

Two-dimensional hybrid organic-inorganic metal halide perovskites offer enhanced stability for perovskite-based applications. Their crystal structure's soft and ionic nature gives rise to strong interactions between charge carriers and ionic rearrangements. Here, we investigate the interaction of photo-generated electrons and ionic polarizations in single-crystal 2D perovskite butylammonium lead iodide, varying the inorganic lammelae thickness in the 2D single crystals. We determined the directionality of the transition dipole moments of the relevant phonon modes (in the 0.3-3 THz range) by angle-and-polarization dependent THz transmission measurements. We find a clear anisotropy of the in-plane photoconductivity, with a 10% reduction along the axis parallel with the transition dipole moment of the most strongly coupled phonon. Detailed calculations, based on Feynman polaron theory, indicate that the anisotropy originates from directional electron-phonon interactions.