Crossing Seam Blockade

TL;DR

This study reveals that crossing seams in electronic states can completely block reaction channels, demonstrated through ab initio simulations of singlet fission in hydrogen chains, offering new insights into controlling photochemical reactions.

Contribution

It uncovers a novel mechanism where electronic crossing seams can inhibit reaction pathways, advancing understanding of excited-state chemical reactivities.

Findings

Singlet fission in H4 hydrogen chain is blocked by crossing seam.

Electronic quantum geometry influences reaction channel accessibility.

Provides a new perspective on controlling photochemical reactions.

Abstract

Electronic degeneracies and near-degeneracies including conical intersections and avoided crossings, typically accompanied by strong vibronic couplings and nonadiabatic transitions, play fundamental roles in photochemical, photophysical and photobiological processes. However, its implications on excited-state chemical reactivities are not fully understood. In this theoretical study, we report a surprising phenomena that an open reaction channel can be completely blocked by a crossing seam in the molecular configuration space. Specifically, by numerically exact ab initio nonadiabatic full quantum geometrical molecular dynamics simulations, we show that the singlet fission channel in the hydrogen chain H4, previously identified as a minimal model for singlet fission, is blocked due to electronic quantum geometry. We provide a chemically intuitive picture to understand this effect. Our results not only reveal a new mechanism for controlling photochemical reactions, but may also elucidate the mechanism of singlet fission.