arXiv subjects

Kristjan Kunnus

Publications and source records attributed to Kristjan Kunnus.

4 recordsLinked to original sources

arXiv2026

The chemRIXS Instrument for the LCLS-II X-Ray Free Electron Laser

The chemRIXS instrument at the Linac Coherent Light Source offers new opportunities for studying solution-phase systems with time-resolved soft X-ray spectroscopy through the recently commissioned high-repetition-rate LCLS-II X-ray free electron laser. The orders-of-magnitude X-ray flux improvement provided by the superconducting accelerator, combined with corresponding advances in the optical laser system and the liquid jet recirculation system, enables studies on dilute systems with high signal-to-noise compared to what was possible with the LCLS-I copper accelerator. These capabilities open up time-resolved X-ray absorption spectroscopy and resonant inelastic X-ray scattering to entirely new classes of samples, as well as enabling the development of new soft X-ray spectroscopies on liquid samples. An overview of the beamline components and the first LCLS-II commissioning results are presented.

physics.ins-det↗

arXiv2025

Tracking Electron, Proton, and Solvent Motion in Proton-Coupled Electron Transfer with Ultrafast X-rays

Proton-coupled electron transfer (PCET) is foundational to catalysis, bioenergetics, and energy conversion, yet capturing and disentangling the coupled motions of electrons, protons, and solvent has remained a major experimental challenge. We combine femtosecond optical spectroscopy, site-specific ultrafast soft X-ray absorption spectroscopy, and time-resolved X-ray scattering with advanced calculations to disentangle the elementary steps of PCET in solution. Using a ruthenium polypyridyl model complex, we directly resolve photoinduced electron redistribution, ligand-site protonation within 100 ps, and the accompanying solvent reorganization. This unified multi-modal approach provides an orbital-level, atomistic picture of PCET, showing how electronic, nuclear, and solvation degrees of freedom can be separated experimentally. Our results establish a general X-ray framework for understanding and ultimately controlling PCET in catalysis, artificial photosynthesis, and biological energy flow.

physics.chem-ph↗

arXiv2019

Tuning Excited State Electron Transfer in Fe Tetracyano-Polypyridyl Complexes

We have investigated photoinduced intramolecular electron transfer dynamics following metal-to-ligand charge-transfer (MLCT) excitation of [Fe(CN)$_4$(2,2'-bipyridine)]$^{2-}$ (1), [Fe(CN)$_4$(2,3-bis(2-pyridyl)pyrazine)]$^{2-}$ (2) and [Fe(CN)$_4$(2,2'-bipyrimidine)]$^{2-}$ (3) complexes in various solvents with static and time-resolved UV-visible absorption spectroscopy and Fe 2p3d resonant inelastic X-ray scattering. We observe $^3$MLCT lifetimes from 180 fs to 67 ps over a wide range of MLCT energies in different solvents by utilizing the strong solvatochromism of the complexes. Intramolecular electron transfer lifetimes governing $^3$MLCT relaxation increase monotonically and (super)exponentially as the $^3$MLCT energy is decreased in 1 and 2 by changing the solvent. This behavior can be described with non-adiabatic classical Marcus electron transfer dynamics along the indirect $^3$MLCT->$^3$MC pathway, where the $^3$MC is the lowest energy metal-centered (MC) excited state. In contrast, the $^3$MLCT lifetime in 3 changes non-monotonically and exhibits a maximum. This qualitatively different behaviour results from direct electron transfer from the $^3$MLCT to the electronic ground state (GS). This pathway involves nuclear tunnelling for the high-frequency polypyridyl skeleton mode ($\hbarω$ = 1530 cm$^{-1}$), which is more displaced for 3 than for either 1 or 2, therefore making the direct pathway significantly more efficient in 3. To our knowledge, this is the first observation of an efficient $^3$MLCT->GS relaxation pathway in an Fe polypyridyl complex. Our study suggests that further extending the MLCT state lifetime requires (1) lowering the $^3$MLCT state energy with respect to the $^3$MC state and (2) suppressing the intramolecular distortion of the electron-accepting ligand in the $^3$MLCT excited state to suppress the rate of direct $^3$MLCT->GS electron transfer.

physics.chem-ph↗

arXiv2019

Origin of vibrational wavepacket dynamics in Fe carbene photosensitizer determined with femtosecond X-ray emission and scattering

Disentangling the dynamics of electrons and nuclei during nonadiabatic molecular transformations remains a considerable experimental challenge. Here we have investigated photoinduced electron transfer dynamics following a metal-to-ligand charge-transfer (MLCT) excitation of the [Fe(bmip)2]2+ photosensitizer, where bmip = 2,6-bis(3-methyl-imidazole-1- ylidine)-pyridine, with simultaneous femtosecond-resolution Fe Kα and K\b{eta} X-ray Emission Spectroscopy (XES) and Wide Angle X-ray Scattering (WAXS). This measurement clearly shows temporal oscillations in the XES and WAXS difference signals with the same 278 fs period oscillation. The oscillatory signal originates from an Fe-ligand stretching mode vibrational wavepacket on a triplet metal-centered (3MC) excited state surface. The vibrational wavepacket is created by 40% of the excited population that undergoes electron transfer from the non-equilibrium MLCT excited state to the 3MC excited state with a 110 fs time constant, while the other 60% relaxes to a 3MLCT excited state in parallel. The sensitivity of the Kα XES spectrum to molecular structure results from core-level vibronic coupling, due to a 0.7% average Fe-ligand bond length difference in the lowest energy geometry of the 1s and 2p core-ionized states. These results highlight the importance of vibronic effects in time-resolved XES experiments and demonstrate the role of metal-centered excited states in the electronic excited state relaxation dynamics of an Fe carbene photosensitizer.

physics.chem-ph↗