arXiv subjects

Jonathan M. Michelsen

Publications and source records attributed to Jonathan M. Michelsen.

5 recordsLinked to original sources

arXiv2025

Correlated Terahertz phonon-ion interactions control ion conduction in a solid electrolyte

Ionic conduction in solids that exceeds 1 mS/cm is predicted to involve coupled phonon-ion interactions in the crystal lattice. Here, we use theory and experiment to measure the possible contribution of coupled phonon-ion hopping modes which enhance Li+ migration in Li0.5La0.5TiO3 (LLTO). The ab initio calculations predict that the targeted excitation of individual TiO6 rocking modes greatly increases the Li+ jump rate as compared to the excitation of vibrational modes associated with heating. Experimentally, coherently driving TiO6 rocking modes via terahertz (THz) illumination leads to a ten-fold decrease in the differential impedance compared to the excitation of acoustic and optical phonons. Additionally, we differentiate the ultrafast responses of LLTO due to ultrafast heating and THz-range vibrations using laser-driven spectroscopy (LUIS), finding a unique long-lived response for the THz-range excitation. These findings provide new insights into coupled ion migration mechanisms, indicating the important role of THz-range coupled phonon-ion hopping modes in enabling fast ion conduction at room temperature.

cond-mat.mtrl-sci↗

arXiv2025

Coherent and Dynamic Small Polaron Delocalization in CuFeO$_{2}$

Small polarons remain a significant bottleneck in the realization of efficient devices using transition metal oxides. Routes to engineer small polaron coupling to electronic states and lattice modes to control carrier localization remain unclear. Here, we measure the formation of small polarons in CuFeO$_{2}$ using transient extreme ultraviolet reflection spectroscopy and compare it to theoretical predictions in realistically parameterized Holstein models, demonstrating that polaron localization depends on its coupling to the high-frequency versus low-frequency components of the phonon bath. We measure that small polaron formation occurs on a comparable ~100 fs timescale to other Fe(III) compounds. After formation, a dynamic delocalization of the small polaron occurs through a coherent lattice expansion between Fe-O layers and charge-sharing with surrounding Fe(IV) states. Our simulations of polaron formation dynamics reveal that two major factors dictate polaron formation timescales: phonon density and reorganization energy distributions between acoustic and optical modes, matching experimental findings. Our work provides a detailed, real-time observation of how electronic-structural coupling in a polaron-host material can be leveraged to suppress polaronic effects for various applications.

cond-mat.mtrl-sci↗

arXiv2022

Ab Initio Calculations of XUV Ground and Excited States for First-Row Transition Metal Oxides

Transient X-ray spectroscopies have become ubiquitous in studying photoexcited dynamics in solar energy materials due to their sensitivity to carrier occupations and local chemical or structural dynamics. The interpretation of solid-state photoexcited dynamics, however, is complicated by the core-hole perturbation and the resulting many-body dynamics. Here, an ab initio, Bethe-Salpeter equation (BSE) approach is developed that can incorporate photoexcited state effects for solid-state materials. The extreme ultraviolet (XUV) absorption spectra for the ground, photoexcited, and thermally expanded states of first row transition metal oxides - $TiO_2, α-Cr_2O_3, β-MnO_2, α-Fe_2O_3, Co_3O_4, NiO, CuO, and ZnO$ - are calculated to demonstrate the accuracy of this approach. The theory is used to decompose the core-valence excitons into the separate components of the X-ray transition Hamiltonian for each of the transition metal oxides investigated. The decomposition provides a physical intuition about the origins of XUV spectral features as well as how the spectra will change following photoexcitation. The method is easily generalized to other K, L, M, and N edges to provide a general approach for analyzing transient X-ray absorption or reflection data.

cond-mat.mtrl-sci↗

arXiv2021

Measuring photoexcited electron and hole dynamics in ZnTe and modeling excited state core-valence effects in transient XUV reflection spectroscopy

Transient XUV spectroscopy is growing in popularity for the measurement of solar fuel and photovoltaic materials as it can separately measure electron and hole energies for multiple elements at once. However, interpretation of transient XUV measurements is complicated by changes in core-valence exciton and angular momentum effects after photoexcitation. Here, we report the photoexcited electron and hole dynamics for ZnTe, a promising material for CO2 reduction, following 400 nm excitation. We apply a newly developed, ab-initio theoretical approach based on density functional theory and the Bethe-Salpeter equation to accurately predict the excited state change in the measured transient XUV spectra. Electrons excited to the conduction band are measured with a thermalization rate of 70 $\pm$ 40 fs. Holes are excited with an average excess energy of ~1 eV and thermalize in 1130 $\pm$ 150 fs. The theoretical approach also allows an estimated assignment of inter- and intra-valley relaxation pathways in k-space using the relative amplitudes of the core-valence excitons.

cond-mat.mtrl-sci↗

arXiv2021

Element-specific electronic and structural dynamics using transient X-ray spectroscopy

Transient X-ray absorption techniques can measure ultrafast dynamics of the elemental edges in a material or multiple layer junction, giving them immense potential for deconvoluting concurrent processes. However, the interpretation of the photoexcited changes to an X-ray edge is not as simple as directly probing a transition with optical or infrared wavelengths. The core hole left by the core-level transition distorts the measured absorption and reflection spectra, both hiding and revealing different aspects of a photo-induced process. In this perspective, we describe the implementation and interpretation of transient X-ray experiments. This description includes a guide of how to choose the best wavelength and corresponding X-ray sources when designing an experiment. As an example, we focus on the rising use of extreme ultraviolet (XUV) spectroscopy for understanding performance limiting behaviors in solar energy materials, such as measurements of polaron formation, electron and hole kinetics, and charge transport in each layer of a metal-oxide-semiconductor junction. The ability of measuring photoexcited carriers in each layer of a multilayer junction could prove particularly impactful in the study of molecules, materials, and their combinations that lead to functional devices in photochemistry and photoelectrochemistry.

cond-mat.mtrl-sci↗