Petr Slavicek

Critical Assessment of Curvature-Driven Surface Hopping Algorithms Trajectory surface-hopping (TSH) methods have become the most used approach in nonadiabatic molecular dynamics. The increasingly popular curvature-driven schemes represent a subset of TSH based on the implicit local diabatization of potential energy surfaces. Their appeal partly stems from compatibility with machine-learning frameworks that often provide only local PES information. Here, we critically assess the limitations of these curvature-based algorithms by examining three challenging scenarios: (i) dynamics involving more than two strongly coupled electronic states; (ii) trivial crossings; and (iii) spurious transitions arising from small discontinuities in multireference potential energy surfaces. Furthermore, we extend the Landau–Zener surface hopping (LZSH) method beyond two-state systems and introduce practical modifications to enhance its robustness. The performance is benchmarked on both low- and higher-dimensional model Hamiltonians, as well as realistic molecular systems treated with ab initio methods. While curvature-driven TSH using the explicit electronic coefficient propagation qualitatively captures the dynamics in most cases, we find no regime where it outperforms LZSH, especially when trivial crossings, multistate crossings, or discontinuities are encountered. Hence, we advocate for using a conceptually simple but solid LZSH method when nonadiabatic couplings are not available.

Curvature-driven methods in photodynamics don’t need NACs or wf derivatives and are gaining traction. We checked cases where they shouldn’t work — and still, Landau-Zener surface hopping comes out on top.

#CompChem

pubs.acs.org/doi/10.1021/...

SF6 is way cheaper than xenon—so why don’t Everest climbers use it for acclimatization?

Richard J. Saykally Festschrift: A Spectroscopic Panorama From Molecular Ions to Liquid Surfaces OR SEARCH CITATIONS

Happy to be part of the Richard J. Saykally Festschrift: A Spectroscopic Panorama From Molecular Ions to Liquid Surfaces

pubs.acs.org/page/jpcafh/...

@pubs.acs.org

PhD position in modelling (time-resolved) photoemission spectra in the condensed phase - MSCA doctoral network LUMIERE In the framework of the EU-funded Marie Skłodowska-Curie Actions Doctoral Network LUMIERE - “Liquid phase Ultrafast photoeMIssion spEctroscopy of nonadiabatic photoREactions in biomimetic systems”, UC...

We're offering a PhD position in our lab as part of the MSCA Lumiere network.

Focus: Modeling time-resolved photoemission in liquid phase, X-ray spectroscopies, and photodynamics.

Learn more and apply here: www.euraxess.cz/jobs/310398

#PhD #ResearchOpportunity #CompChem

My dentist asked about the patron saint of chemists, and embarrassingly, I didn’t know. Turns out, it’s Albertus Magnus, likely the discoverer of arsenic. Canonized in 1931, named patron in 1941, centuries after his 1280 death. Not sure what he did in the meantime. Ready for my next dentist visit!

The new #CECAM program is now live!
76 exciting workshops, schools and conferences will be held across the network between April 2025 and March 2026!
Explore our activities and apply to participate at: www.cecam.org/program

Selecting Initial Conditions for Trajectory-Based Nonadiabatic Simulations ConspectusPhotochemical reactions have always been the source of a great deal of mystery. While classified as a type of chemical reaction, no doubts are allowed that the general tenets of ground-state...

How far can nonadiabatic simulations go with proper initial state sampling? We comment on the strategies in the recent Accounts of Chemical Research paper
pubs.acs.org/doi/10.1021/...

#NonadiabaticDynamics #SimulationScience #compchem
@insilphotochem.bsky.social @pubs.acs.org