Engineering topics

Liekhus-Schmaltz, Chelsea

Publications and source records attributed to Liekhus-Schmaltz, Chelsea.

4 records

DOE OSTI2022

Femtosecond X-ray Spectroscopy Directly Quantifies Transient Excited-State Mixed Valency

Quantifying charge delocalization associated with short-lived photoexcited states of molecular complexes in solution remains experimentally challenging, requiring local element specific femtosecond experimental probes of time-evolving electron transfer. In this study, we quantify the evolving valence hole charge distribution in the photoexcited charge transfer state of a prototypical mixed valence bimetallic iron–ruthenium complex, [(CN) 5 Fe II CNRu III (NH 3 ) 5 ]-, in water by combining femtosecond X-ray spectroscopy measurements with time-dependent density functional theory calculations of the excited-state dynamics. We estimate the valence hole charge that accumulated at the Fe atom to be 0.6 ± 0.2, resulting from excited-state metal-to-metal charge transfer, on an ~ 60 fs time scale. Our combined experimental and computational approach provides a spectroscopic ruler for quantifying excited-state valency in solvated complexes.

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DOE OSTI2021

Spectral Signatures of Ultrafast Excited-State Intramolecular Proton Transfer from Computational Multi-edge Transient X-ray Absorption Spectroscopy

Excited state intramolecular proton transfer (ESIPT) is a fundamental chemical process with several applications. Ultrafast ESIPT involves coupled electronic and atomic motions and has been primarily studied using femtosecond optical spectroscopy. X-ray spectroscopy is particularly useful because it is element-specic and enables direct, individual probes of the proton donating and accepting atoms. Here, we report a computational study to resolve the ESIPT in 10-Hydroxybenzo[h]quinoline (HBQ), an intramolecularly hydrogen bonded compound, using time-dependent density functional theory combined with ab initio molecular dynamics (AIMD) and time-resolved X-ray absorption spectroscopy (XAS) computations to track the ultrafast excited-state dynamics. Overall, our results reveal clear X-ray spectral signatures of coupled electronic and atomic motions during and following ESIPT at the oxygen and nitrogen K-edge paving the way for future experiments at X-ray free electron lasers.

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DOE OSTI2021

Direct observation of coherent femtosecond solvent reorganization coupled to intramolecular electron transfer

It is well known that the solvent plays a critical role in ultrafast electron-transfer reactions. However, solvent reorganization occurs on multiple length scales, and selectively measuring short-range solute–solvent interactions at the atomic level with femtosecond time resolution remains a challenge. Here we report femtosecond X-ray scattering and emission measurements following photoinduced charge-transfer excitation in a mixed-valence bimetallic (Fe ii Ru iii ) complex in water, and their interpretation using non-equilibrium molecular dynamics simulations. Combined experimental and computational analysis reveals that the charge-transfer excited state has a lifetime of 62 fs and that coherent translational motions of the first solvation shell are coupled to the back electron transfer. Overall, our molecular dynamics simulations identify that the observed coherent translational motions arise from hydrogen bonding changes between the solute and nearby water molecules upon photoexcitation, and have an amplitude of tenths of ångströms, 120–200 cm -1 frequency and ~100 fs relaxation time. This study provides an atomistic view of coherent solvent reorganization mediating ultrafast intramolecular electron transfer.

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DOE OSTI2020

Strictly non-adiabatic quantum control of the acetylene dication using an infrared field

We demonstrate the existence of a strictly non-adiabatic control pathway in deprotonation of the acetylene dication. This pathway is identified experimentally by measuring a kinetic energy shift in an ion coincidence experiment. We use a time dependent Schrödinger equation simulation to identify which properties most strongly affect our control. We find that resonant control around conical intersections is limited by the speed of non-adiabatic dynamics.

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