arXiv subjects

Michael Schuurman

Publications and source records attributed to Michael Schuurman.

4 recordsLinked to original sources

arXiv2026

Resolving electronic evolution during bond dissociation

Coupled electronic and nuclear motions govern chemical reactions, yet resolving how electronic structure evolves during bond dissociation remains a central challenge. Here we investigate the photodissociation of Br2 using correlated photoelectron photoion coincidence measurements. A 400 nm pulse initiates dissociation, while strong field ionization probes the evolving molecular system. Coincident measurement of three dimensional photoion and photoelectron momenta provides simultaneous access to the internuclear separation and the accompanying electronic evolution. We identify multiple distinct stages of electronic evolution during bond dissociation. The reshaping of the ionizing molecular orbital occurs first, followed by redistribution and localization of the electronic charge density, and finally by the gradual decay of residual electronic coherence between the separating atomic centers. Between the molecular and atomic limits, we observe an intermediate bond-breaking state in which localized atomic character coexists with a partially delocalized electronic response. By combining correlated observables with semiclassical modelling, we resolve the temporal ordering of these coupled electronic and nuclear processes and determine their associated dynamical timescales. These results demonstrate how correlated momentum observables can disentangle different aspects of the molecular-to-atomic transition.

physics.chem-ph↗

arXiv2026

Frequency-resolved ultrafast electron diffraction: visualizing vibrational dynamics in frequency- and real-space

Ultrafast electron diffraction (UED) provides direct information on changes in molecular structure following photoexcitation, but identifying the individual vibrational motions contributing to these dynamics remains challenging. Here, we introduce frequency-resolved UED, where Fourier transformation of the time-dependent difference pair distribution function ($Δ$PDF) gives a two-dimensional frequency-distance representation of the structural dynamics. We apply this approach to allene and 1,2-butadiene following photoexcitation to the $S_1(ππ^*)$ state at 200 nm, using electron scattering signals simulated from previously-published ab initio multiple spawning trajectories (S. P. Neville et al., J. Chem. Phys., 2016, 144, 014305). We identify C=C stretching and CCC bending motions and the internuclear distances over which they contribute, and separate overlapping CH$_2$ vibrational motions. By changing the pump-probe delay range used for the Fourier transform, we identify when specific frequency components contribute during the excited-state dynamics. Methyl substitution reduces the C=C stretching and CCC bending frequencies and introduces an additional frequency component in 1,2-butadiene during the first 90 fs. We further show the importance of sub-20-fs, and ultimately few-femtosecond, temporal resolution for retrieving these frequency components. Frequency-resolved UED therefore provides the vibrational frequencies, internuclear distances, and reaction times associated with photoinduced structural dynamics.

physics.chem-ph↗

arXiv2026

Operator Entanglement in Quantum Dynamics Simulations: Formalism and Analysis Tools

We review the framework of operator Hilbert space and introduce the one- and two-particle super reduced density matrices (1-SRDMs and 2-SRDMs), as well as the super mutual information (SMI). The eigenvectors of the 1-SRDMs define what we term natural single particle operator bases, and provide a way to compress vibrational and vibronic Hamiltonians with controlled error. The SMI is defined from the operator entanglement entropy of the 1-SRDMs and 2-SRDMs, and captures the correlation between operators acting on different one-mode subspaces, which may be used to reveal and quantify both direct and indirect couplings that might otherwise be difficult to extract. Efficient numerical approaches for the calculation of SRDMs and the SMI are developed and applied to a set of prototypical vibrational and vibronic Hamiltonians, as well as approximations to the corresponding time-evolution operators. Through this, we demonstrate that: (i) commonly used vibronic Hamiltonians are amenable to extremely high levels of compression without compromising accuracy, and; (ii) SMI analysis can be used to systematically and quantitatively reveal both direct and indirect couplings that might otherwise be difficult to extract, including indirect couplings of vibrational modes via intermediary electronic-vibrational interactions.

quant-ph↗

arXiv2022

A Laboratory Frame Density Matrix for Ultrafast Quantum Molecular Dynamics

In most cases the ultrafast dynamics of resonantly excited molecules are considered, and almost always computed in the molecular frame, while experiments are carried out in the laboratory frame. Here we provide a formalism in terms of a lab frame density matrix which connects quantum dynamics in the molecular frame to those in the laboratory frame, providing a transparent link between computation and measurement. The formalism reveals that in any such experiment, the molecular frame dynamics vary for molecules in different orientations and that certain coherences which are potentially experimentally accessible are rejected by the orientation-averaged reduced vibronic density matrix. Instead, Molecular Angular Distribution Moments (MADMs) are introduced as a more accurate representation of experimentally accessible information. Furthermore, the formalism provides a clear definition of a molecular frame quantum tomography, and specifies the requirements to perform such a measurement enabling the experimental imaging of molecular frame vibronic dynamics. Successful completion of such a measurement fully characterizes the molecular frame quantum dynamics for a molecule at any orientation in the laboratory frame.

physics.chem-ph↗