Reduced-Dimensional Reaction-Space Analysis of a Trispericyclic Reaction by ReSPer.
- 1Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo, Japan.
- 2Institute for Quantum Chemical Exploration, Tokyo, Japan.
- 3Institute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido University, Sapporo, Japan.
Abstract
Post-transition-state bifurcation, which plays a critical role in determining product selectivity, has gained significant attention in synthetic chemistry. A trispericyclic reaction has been reported, producing three different cycloadducts from a single transition state structure. Its mechanisms have been examined through elementary reaction processes and dynamical trajectory simulations. However, because the relevant static reaction paths and dynamical trajectories are embedded in a high-dimensional configurational space, their mutual relationships and the potential-energy features governing product branching are difficult to interpret without choosing a limited set of reaction coordinates. In this study, we use the Reaction Space Projector (ReSPer) method, which mathematically constructs a reduced-dimensional chemical reaction space from a set of reference structures to uncover the dynamical branching mechanisms of the trispericyclic reaction. The two-dimensional reaction space reveals that the reaction path network in the configurational space forms an arrowhead-shaped landscape, differing from the traditionally recognized fork-shaped landscape. Projecting dynamical trajectories onto the two-dimensional reaction space shows that dynamic branching processes occur near the shoulder in the energy profile along the main reaction path from the transition state to the major cycloadduct, where the potential valley orthogonal to the reaction direction flattens out. These results demonstrate that ReSPer provides a useful reduced-dimensional representation for relating static reaction-path networks to dynamical branching trajectories, and may offer new descriptors for future branching-ratio prediction in pericyclic reactions.
Related
- Molybdenum Disulfide Bilayers Hybridized With Reduced Graphene Oxide Nanosheets for Enhanced Hydrogen Evolution Reaction
- Elucidating the Role of Energy- and Electron-Transfer Processes and the Route to Highly Reduced Products in the Dual IrIII/FeIII Photocatalyzed CO2 Reduction Reaction.
- Synergistic Multi-Heteroatom Doping in Three-Dimensional-Porous Iron Single-Atom Catalysts for Enhanced Oxygen Reduction Reaction
- Freestanding FeS2-Integrated Reduced Graphene Oxide Aerogels Enhance Cathode-to-Cell Electron Transfer in Three-Dimensional Living Cathodes
- Integer electron-count cuts in variational second-order reduced-density-matrix theory. I. Molecular dissociation with fixed real-space and orbital partitions
BibTeX
@article{tsutsumi2026reduceddimensional,
title = {{Reduced-Dimensional Reaction-Space Analysis of a Trispericyclic Reaction by ReSPer.}},
author = {Takuro Tsutsumi and Akifumi Fujita and Yuriko Ono and Tetsuya Taketsugu},
journal = {Journal of computational chemistry},
year = {2026},
month = nov,
doi = {10.1002/jcc.70539},
url = {https://europepmc.org/article/MED/42973107},
note = {CC BY},
}
RIS
TY - JOUR
TI - Reduced-Dimensional Reaction-Space Analysis of a Trispericyclic Reaction by ReSPer.
AU - Takuro Tsutsumi
AU - Akifumi Fujita
AU - Yuriko Ono
AU - Tetsuya Taketsugu
PY - 2026
DA - 2026/11/01
JO - Journal of computational chemistry
DO - 10.1002/jcc.70539
UR - https://europepmc.org/article/MED/42973107
AB - Post-transition-state bifurcation, which plays a critical role in determining product selectivity, has gained significant attention in synthetic chemistry. A trispericyclic reaction has been reported, producing three different cycloadducts from a single transition state structure. Its mechanisms have been examined through elementary reaction processes and dynamical trajectory simulations. However, because the relevant static reaction paths and dynamical trajectories are embedded in a high-dimensional configurational space, their mutual relationships and the potential-energy features governing product branching are difficult to interpret without choosing a limited set of reaction coordinates. In this study, we use the Reaction Space Projector (ReSPer) method, which mathematically constructs a reduced-dimensional chemical reaction space from a set of reference structures to uncover the dynamical branching mechanisms of the trispericyclic reaction. The two-dimensional reaction space reveals that the reaction path network in the configurational space forms an arrowhead-shaped landscape, differing from the traditionally recognized fork-shaped landscape. Projecting dynamical trajectories onto the two-dimensional reaction space shows that dynamic branching processes occur near the shoulder in the energy profile along the main reaction path from the transition state to the major cycloadduct, where the potential valley orthogonal to the reaction direction flattens out. These results demonstrate that ReSPer provides a useful reduced-dimensional representation for relating static reaction-path networks to dynamical branching trajectories, and may offer new descriptors for future branching-ratio prediction in pericyclic reactions.
SN - 0192-8651
SN - 1096-987X
ER -