DOE OSTI · 3007439
Tracing Long-Lived Atomic Coherences Generated via Molecular Conical Intersections
Abstract
Accessing coherences is key to fully understand and control ultrafast dynamics of complex quantum systems like molecules. Most photochemical processes are mediated by conical intersections, which generate coherences between electronic states in molecules. We show with accurate calculations performed on gas-phase methyl iodide that electronic coherences of spin-orbit-split states persist in atomic iodine after dissociation. Our simulation predicts a maximum magnitude of vibronic coherence in the molecular regime of 0.75% of the initially photoexcited state population. Upon dissociation, one-third of this coherence magnitude is transferred to a long-lived atomic coherence where vibrational decoherence can no longer occur. To trace these dynamics, we propose a tabletop experimental approach—heterodyned attosecond four-wave-mixing spectroscopy. This technique can temporally resolve small electronic coherence magnitudes and reconstruct the full complex coherence function via phase cycling. Hence, heterodyned attosecond four-wave-mixing spectroscopy leads the way to a complete understanding and optimal control of spin-orbit-coupled electronic states in photochemistry.
Explore related subjects
Keep this discovery
Explore connections, maps & timelines
Rupprecht, Patrick [University of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)] (ORCID:000000026491793X), Montorsi, Francesco [University of Bologna (Italy)] (ORCID:0000000210584770), Xu, Lei [Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)] (ORCID:0000000339335521), Puskar, Nicolette G. [University of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)] (ORCID:0000000215373753), Garavelli, Marco [University of Bologna (Italy)] (ORCID:000000020796289X), Mukamel, Shaul [University of California, Irvine, CA (United States)] (ORCID:0000000260153135), Govind, Niranjan [Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); University of Washington, Seattle, WA (United States)] (ORCID:000000033625366X), Neumark, Daniel M. [University of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)] (ORCID:0000000237629473), Keefer, Daniel [Max Planck Institute for Polymer Research, Mainz (Germany)] (ORCID:0000000159415567), Leone, Stephen R. [University of California, Berkeley, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)] (ORCID:0000000318191338). 2025-12-05. Tracing Long-Lived Atomic Coherences Generated via Molecular Conical Intersections. https://doi.org/10.1103/6bfk-mgpn
Cite the original work for its findings. Save a collection to share your selection of sources.