arXiv subjects

Lina Fransén

Publications and source records attributed to Lina Fransén.

4 recordsLinked to original sources

arXiv2026

Femtosecond Nonadiabatic Confinement of Molecular Dication Yield

Doubly charged molecular cations often carry signatures of electronic correlation and electron-nuclear entanglement present in the parent cation. Here, we produce ethylene dications using a combination of an extreme ultraviolet pump and near-infrared probe pulses, observing a peak in the dication yield at a pump-probe delay of approximately 15 fs. Ab-initio calculations, which explicitly take into account coupled electron-nuclear dynamics induced by the pump and the multiphoton nature of the probe-induced ionization step, reproduced the observed delay in the yield. It originates from resonant enhancement of the multiphoton ionization of the electronically excited ethylene cation as the carbon-carbon double bond expands. However, this effect is tempered by rapid nonadiabatic relaxation of the excited ionic states. Our results suggest a general mechanism whereby ultrafast nonadiabatic relaxation of a molecular ion can compete with its strong-field ionization rate, confining the dication yield to a narrow temporal window of a few femtoseconds.

physics.chem-ph↗

arXiv2025

Attochemical control of nuclear motion despite fast electronic decoherence

Short-in-time, broad-in-energy attosecond or few-femtosecond pulses can excite coherent superpositions of several electronic states in molecules. This results in ultrafast charge oscillations known as charge migration. A key open question in the emerging field of attochemistry is whether these electron dynamics, which due to decoherence often last only for a few femtoseconds, can influence longer-time scale nuclear rearrangements. Herein, we address this question through full-dimensional quantum dynamics simulations of the coupled electron-nuclear dynamics initiated by ionization and coherent excitation of ethylene. The simulations of this prototype organic chromophore predict electronic coherences with half-lives of less than 1 fs. Despite their brevity, these electronic coherences induce vibrational coherences along the derivative coupling vectors that persist for at least 50 fs. These results suggest that short-lived electronic coherences can impart long-lasting legacies on nuclear motion, a finding of potential importance to the interpretation of attosecond experiments and the development of strategies for attochemical control.

physics.chem-ph↗

arXiv2025

Tracking photophysical relaxation in spiropyran with simulated time-resolved X-ray absorption spectroscopy

Spiropyran is a prototype photoswitch that undergoes photoinduced ring-opening via C-O bond fission. The quantum yield for this photochemical reaction is low, with photophysical relaxation being the dominant process. Previous theoretical studies have suggested that photophysical relaxation proceeds via cleavage and subsequent reformation of a C-N bond. However, experimental evidence for this mechanism is lacking; most time-resolved studies have probed in the ultraviolet-visible domain, where C-N bond fission is unlikely to leave clear signatures. Here, we use non-adiabatic dynamics simulations in conjunction with X-ray absorption spectroscopic calculations to investigate the possibility of tracking the photophysical relaxation in spiropyran with time-resolved X-ray absorption spectroscopy at the nitrogen K-edge. The simulations predict that cleavage of the C-N bond results in a transient red-shift of the X-ray absorption. These results indicate a potential experimental route to gain a mechanistic understanding of the efficient photophysical relaxation that limits the efficiency of spiropyran-based photochromic systems.

physics.chem-ph↗

arXiv2024

Dissociation and isomerization following ionization of ethylene: insights from non-adiabatic dynamics simulations

Photoionized and electronically excited ethylene \ce{C2H4+} can undergo \ce{H}-loss, \ce{H2}-loss, and ethylene-ethylidene isomerization, where the latter entails a hydrogen migration. Recent pioneering experiments with few-femtosecond extreme ultraviolet pulses and complementary theoretical studies have shed light on the photodynamics of this prototypical organic cation. However, no theoretical investigation based on dynamics simulations reported to date has described the mechanisms and time scales of dissociation and isomerization. Herein, we simulate the coupled electron-nuclear dynamics of ethylene following vertical ionization and electronic excitation to its four lowest-lying cationic states. The electronic structure is treated at the CASSCF level, with an active space large enough to describe bond breaking and formation. The simulations indicate that dissociation and isomerization take place mainly on the cationic ground state and allow the probing of previous hypotheses concerning the correlation between the photochemical outcome and the traversed conical intersections. The results, moreover, support the long-standing view that \ce{H2}-loss may occur from the ethylidene form. However, the ethylene-ethylidene isomerization time predicted by the simulations is considerably longer than those previously inferred from indirect experimental measurements.

physics.chem-ph↗