Time-resolved Rydberg dynamics in molecules
Abstract
We develop a general theoretical framework for the ultrafast dynamics of coherently populated autoionizing Rydberg states in molecules, whose coherent decay results in asymmetric Fano line shapes produced by interference between resonant autoionization and direct ionization. The asymmetric line shapes form in the photoelectron continuum during the autoionization lifetime of the decreasing Rydberg population. By parameterizing autoionization resonances and solving the time-dependent Schrödinger equation, we model the buildup of the Fano profile together with the decline of the coherently excited Rydberg-state population. We compare our calculated photoelectron yields with the XUV-pump--IR-probe photoemission experiment of Biswas et al., Phys. Rev. A 110, 043106 (2024), in which neutral ground-state CO2 molecules are excited by an XUV pulse to the Henning sharp and diffuse Rydberg series and subsequently ionized by the delayed IR pulse. Based on our numerically modeled photoelectron yields, we analyze two complementary processes: (i) photoemission into the X2Πg continuum of residual CO2+ ions, which exposes interferences between direct photoionization and excited-state autoionization, and (ii) IR-induced photoemission into the CO2+[B2Σu+] continuum, which reveals quantum beats between Rydberg states. Our close-coupling model provides a versatile, extendable framework for tracking molecular Rydberg-state relaxation and, more generally, light-driven coherent dynamics in complex quantum systems.
Related
- Temporal Weight-Position Mapping: time-resolved parameter dominance of electron dynamics in nonlinear Thomson scattering
- Mediating gates between polar molecules using microwave-dressed Rydberg atoms
- Observation of s-p Coupling in Ultralong-Range Rydberg Molecules
- Ultrafast internal dynamics of chiral domain walls probed by time-resolved XRMS
- Hierarchical quasiparticle dynamics in antiferromagnets revealed by time- and momentum-resolved X-ray scattering.
BibTeX
@misc{saydanzad2026timeresolved,
title = {{Time-resolved Rydberg dynamics in molecules}},
author = {Erfan Saydanzad and Van-Hung Hoang and Uwe Thumm},
howpublished = {arXiv},
year = {2026},
month = oct,
doi = {10.48550/arxiv.2610.27286},
eprint = {2610.27286},
archivePrefix = {arXiv},
url = {https://arxiv.org/abs/2610.27286},
}
RIS
TY - UNPB
TI - Time-resolved Rydberg dynamics in molecules
AU - Erfan Saydanzad
AU - Van-Hung Hoang
AU - Uwe Thumm
PY - 2026
DA - 2026/10/19
PB - arXiv
DO - 10.48550/arxiv.2610.27286
UR - https://arxiv.org/abs/2610.27286
AB - We develop a general theoretical framework for the ultrafast dynamics of coherently populated autoionizing Rydberg states in molecules, whose coherent decay results in asymmetric Fano line shapes produced by interference between resonant autoionization and direct ionization. The asymmetric line shapes form in the photoelectron continuum during the autoionization lifetime of the decreasing Rydberg population. By parameterizing autoionization resonances and solving the time-dependent Schrödinger equation, we model the buildup of the Fano profile together with the decline of the coherently excited Rydberg-state population. We compare our calculated photoelectron yields with the XUV-pump--IR-probe photoemission experiment of Biswas et al., Phys. Rev. A 110, 043106 (2024), in which neutral ground-state CO_2 molecules are excited by an XUV pulse to the Henning sharp and diffuse Rydberg series and subsequently ionized by the delayed IR pulse. Based on our numerically modeled photoelectron yields, we analyze two complementary processes: (i) photoemission into the X^2Π_g continuum of residual CO_2^+ ions, which exposes interferences between direct photoionization and excited-state autoionization, and (ii) IR-induced photoemission into the CO_2^+[B^2Σ_u^+] continuum, which reveals quantum beats between Rydberg states. Our close-coupling model provides a versatile, extendable framework for tracking molecular Rydberg-state relaxation and, more generally, light-driven coherent dynamics in complex quantum systems.
ER -