Exploring non-adiabaticity to CO reduction reaction through ab initio molecular dynamics simulation

Zheng, Fan; Wang, Lin-wang

doi:10.1063/5.0002318

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Exploring non-adiabaticity to CO reduction reaction through ab initio molecular dynamics simulation

Zheng, Fan·Wang, Lin-wang

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Abstract

Non-adiabatic chemical reaction refers to the electronic excitation during reactions. This effect cannot be modeled by the ground-state Born-Oppenheimer molecular dynamics (BO-MD), where the electronic structure is at the ground state for every step of ions' movement. Although the non-adiabatic effect has been explored extensively in gas phase reactions, its role in electrochemical reactions, such as water splitting and CO 2 reduction, in electrolyte has been rarely explored. On the other hand, electrochemical reactions usually involve electron transport; thus, a non-adiabatic process can naturally play a significant role. In this work, using one-step CO 2 reduction as an example, we investigated the role of the non-adiabatic effect in the reaction. The reaction barriers were computed by adiabatic BO-MD and non-adiabatic real-time time dependent density functional theory (rt-TDDFT). We found that by including the non-adiabatic effect, rt-TDDFT could increase the reaction barrier up to 6% compared to the BO-MD calculated barrier when the solvent model is used to represent water. Simulations were carried out using explicit water molecules around the reaction site under different overpotentials, and similar non-adiabatic effects were found.

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY Electronic excitation adiabatic process chemical physics electrochemical reactions electrolytes electronic transport molecular dynamics non-adiabatic molecular dynamics real-time time-dependent density-functional theory

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Zheng, Fan, Wang, Lin-wang. 2020-04-21. Exploring non-adiabaticity to CO reduction reaction through ab initio molecular dynamics simulation. https://doi.org/10.1063/5.0002318

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