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arXiv:2512.16132

Multi-messenger tracking of coherence loss during bond breaking

Tian Wang, Nida Haram, Zack Dube, Kyle A. Hamer, Yonghao Mi, Fatemeh Karimi, Andrei Yu. Naumov, Giulio Vampa, Caterina Vozzi, Xiaojun Liu, Albert Stolow, Michael Schuurman, Nicolas Douguet, David Villeneuve, Paul B. Corkum, Andre Staudte

physics.chem-phphysics.atom-phphysics.opticsquant-phSubmitted Dec 18, 2025• Announced Dec 19, 2025
v1 · Dec 18, 2025v2 · Sep 15, 2026
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Abstract

Coupled electronic and nuclear motions govern chemical reactions, yet disentangling their interplay during bond rupture remains challenging. Here we follow the light-induced fragmentation of Br$_2$ using a coincidence-based multi-messenger approach. A UV pulse prepares the dissociative state, and strong-field ionization probes the evolving system. Coincident measurement of three-dimensional photoion and photoelectron momenta provides real-time access to both the instantaneous internuclear separation and the accompanying reorganization of the electronic structure, allowing us to determine the timescale of bond breaking. We find that electronic rearrangement concludes well before the nuclei reach the bond-breaking distance, revealing a hierarchy imposed by electron-nuclear coupling. Supported by semiclassical modelling, the results show that the stretched Br$_2$ molecule behaves as a two-centre interferometer in which the loss of coherence between atomic centres encodes the coupled evolution of electrons and nuclei. Our work establishes a general framework for imaging ultrafast electron-nuclear dynamics in molecules.

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Coupled electronic and nuclear motions govern chemical reactions, yet disentangling their interplay during bond rupture remains challenging. Here we follow the light-induced fragmentation of Br2_22​ using a coincidence-based multi-messenger approach. A UV pulse prepares the dissociative state, and strong-field ionization probes the evolving system. Coincident measurement of three-dimensional photoion and photoelectron momenta provides real-time access to both the instantaneous internuclear separation and the accompanying reorganization of the electronic structure, allowing us to determine the timescale of bond breaking. We find that electronic rearrangement concludes well before the nuclei reach the bond-breaking distance, revealing a hierarchy imposed by electron-nuclear coupling. Supported by semiclassical modelling, the results show that the stretched Br2_22​ molecule behaves as a two-centre interferometer in which the loss of coherence between atomic centres encodes the coupled evolution of electrons and nuclei. Our work establishes a general framework for imaging ultrafast electron-nuclear dynamics in molecules.
Abstract Photoionization of a weakly bound van-der-Waals dimer, composed of two atomic speciesAandB, is studied theoretically. AtomAcan be ionized either directly or via an indirect two-center channel, where atomBis first resonantly photoexcited and, afterwards, transfers the excitation energy via long-range electron–electron correlations radiationlessly to atomA, causing its ionization. By taking the vibrational nuclear motion of the dimer during the process into account, we analyze the contributions to the photoionization cross section from bound and dissociative molecular states in the final A+ –Bsystem. For the specific example of a LiHe dimer we show (a) that substantial contributions to both ionization mechanisms result from dissociative Li ++ He states and (b) that the two-center pathway strongly dominates over the direct photoionization channel for photon energies close to one of the molecular LiHe resonances.
In a double-slit experiment with a bipartite system, the visibility of interference fringes depends on the availability of which-way information. Here, we report a Bell-like state of photoelectron and residual ion in the multiphoton dissociative ionization of the D2_22​ molecule. Evidence for entanglement is provided by the correlated emission directions of photoelectron and ion, which is observed using a COLTRIMS reaction microscope. In the presence of this correlation, the holographic interference fringes contained in the photoelectron momentum distributions are suppressed, indicating the existence of which-way information. The interference pattern persists when a single ionic state is populated and thus no which-way information is available. The experimental observations and conclusions are supported by the numerical solution of the electronic-nuclear time-dependent Schrödinger equation. Our work demonstrates that coincidence spectroscopy of ions and electrons is a powerful method for studying fundamental concepts of quantum information science within the context of ultrafast light-matter interactions.
The ion momentum distribution in the x-ray-induced dissociative photoionization of molecules is investigated, treating the ionization analytically under the Born-Oppenheimer approximation and simulating numerically the ion motion via the Schrödinger equation. The ion-photoelectron entanglement transfers information of the electronic interference to the ion dynamics. As a consequence, the ion momentum distributions of dissociative molecular photoionization present Young's double-slit interference when the photoelectron emission angle is fixed. We demonstrate that double-slit interference signatures persist in the ion longitudinal momentum shift even when the information of the correlated photoelectron is lost, which is the case for heteronuclear molecules when an additional photoelectron recoil momentum arises due to the different ion masses. For the case of sequential double ionization, we show that double-slit interference in the ion dynamics can be utilized for coherent control of the molecular dynamics.
Traditional x-ray photoelectron spectroscopy (XPS) relies upon a direct mapping between the photoelectron binding energies and the local chemical environment, which is well-characterized by an electrostatic partial charges model for systems in equilibrium. However, the extension of this technique to out-of-equilibrium systems has been hampered by the lack of x-ray sources capable of accessing multiple atomic sites with high spectral and temporal resolution, as well as the lack of simple theoretical procedures to interpret the observed signals. In this work we employ multi-site XPS with a narrowband femtosecond x-ray probe to unravel different ultrafast dissociation processes of a polyatomic molecule, fluoromethane (CH3_{3}3​F). We show that XPS can follow the cleavage of both the C-F and C-H bonds in real time, despite these channels lying close in binding energy. Additionally, we apply the partial charges model to describe these dynamics, and verify this extension with both advanced ab-initio calculations and experimental data. These results enable the application of this technique to out-of-equilibrium systems of higher complexity, by correlating real-time information from multiple atomic sites and interpreting the measurements through a viable theoretical modelling.
Photoassociation in laser-assisted collisions of ultracold alkali atoms has been used recently to perform high-precision spectroscopy of very-long-range states. Rovibrational spectra close to the Na(3 2^{2}2S)+Na∗{\mathrm{Na}}^{\mathrm{*}}Na∗(3 2^{2}2P3/2{\mathit{P}}_{3/2}P3/2​) dissociation limit have been obtained by monitoring an enhanced Na2+{\mathrm{Na}}_{2}^{+}Na2+​ ion signal. We propose the use of pump-probe techniques to study the dynamics of the ionization process. At very large distances (typically 70 a.u.) two colliding Na atoms absorb a photon and form a coherent vibrational wave packet. We follow the packet in time and probe two possible mechanisms that are proposed to yield molecular ions: photoionization, where the second photon is absorbed at a small internuclear distance R directly ionizing the molecule, and associative ionization with excitation at intermediate R to the nuclear continuum of a doubly excited state followed by a half collision and autoionization at small R. The latter event can also lead to dissociation of the complex. The two mechanisms lead to distinct differences in the ion signals as a function of delay time between the pump and the probe pulses. Estimates of the ion rates to be expected in actual pump-probe experiments are given, which tend to favor the autoionization mechanism as the dominant reaction path.
Using high-order harmonic attosecond pulse trains, we investigate the photoionization dynamics and transient electronic structure of a helium atom in the presence of moderately strong (∼10(12) W cm(-2)) femtosecond laser pulses. We observe quantum interferences between photoexcitation paths from the ground state to different laser-dressed Floquet state components. As the intensity ramps on femtosecond time scales, we observe switching between ionization channels mediated by different atomic resonances. Using precision measurements of ion yields and photoelectron distributions, the quantum phase difference between interfering paths is extracted for each ionization channel and compared with simulations. Our results elucidate photoionization mechanisms in strong fields and open the doors for photoabsorption or photoionization control schemes.