Mode-Specific Dynamics of CO2 Hydrogenation on Copper: The Hidden Role of Molecular Rotation
Abstract
Catalytic hydrogenation of CO2 to formate on copper is a key elementary step for CO2 utilization. Previous experimental and theoretical studies suggested an Eley-Rideal mechanism for this reaction, promoted by bending vibrational excitation, yet direct state resolved evidence remains lacking. Here, we present first-principles dynamical predictions for CO2 hydrogenation on Cu(111) based on an accurate full-dimensional neural network potential energy surface. Our calculations near-quantitatively reproduce the measured reaction probabilities, including their nozzle-temperature and incidence-energy dependence. Our state-resolved results indicate that while vibrational excitation of the bending mode enhances reactivity, it alone cannot account for the observed reactivity increase with nozzle temperature. Instead, rotational excitation plays a dominant role, mainly attributable to the significant change in anisotropy of the molecular polar orientation as CO2 accesses the transition state. This mode-specific insight reinforces the hidden role of rotation in surface reactivity, opening new avenues for state-selective control of CO2 hydrogenation on heterogenous catalysts.
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BibTeX
@misc{xia2026modespecific,
title = {{Mode-Specific Dynamics of $\textCO_2$ Hydrogenation on Copper: The Hidden Role of Molecular Rotation}},
author = {Junfan Xia and Zhikai Jiang and Yaolong Zhang and Bo Peng and Hua Guo and Bin Jiang},
howpublished = {arXiv},
year = {2026},
month = aug,
doi = {10.48550/arxiv.2608.27850},
eprint = {2608.27850},
archivePrefix = {arXiv},
url = {https://arxiv.org/abs/2608.27850},
}
RIS
TY - UNPB
TI - Mode-Specific Dynamics of CO_2 Hydrogenation on Copper: The Hidden Role of Molecular Rotation
AU - Junfan Xia
AU - Zhikai Jiang
AU - Yaolong Zhang
AU - Bo Peng
AU - Hua Guo
AU - Bin Jiang
PY - 2026
DA - 2026/08/31
PB - arXiv
DO - 10.48550/arxiv.2608.27850
UR - https://arxiv.org/abs/2608.27850
AB - Catalytic hydrogenation of CO_2 to formate on copper is a key elementary step for CO_2 utilization. Previous experimental and theoretical studies suggested an Eley-Rideal mechanism for this reaction, promoted by bending vibrational excitation, yet direct state resolved evidence remains lacking. Here, we present first-principles dynamical predictions for CO_2 hydrogenation on Cu(111) based on an accurate full-dimensional neural network potential energy surface. Our calculations near-quantitatively reproduce the measured reaction probabilities, including their nozzle-temperature and incidence-energy dependence. Our state-resolved results indicate that while vibrational excitation of the bending mode enhances reactivity, it alone cannot account for the observed reactivity increase with nozzle temperature. Instead, rotational excitation plays a dominant role, mainly attributable to the significant change in anisotropy of the molecular polar orientation as CO_2 accesses the transition state. This mode-specific insight reinforces the hidden role of rotation in surface reactivity, opening new avenues for state-selective control of CO_2 hydrogenation on heterogenous catalysts.
ER -