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| Main Authors: | , |
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| Format: | Preprint |
| Published: |
2025
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| Subjects: | |
| Online Access: | https://arxiv.org/abs/2503.03136 |
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| _version_ | 1866909525410316288 |
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| author | Altman, Aaron R. da Jornada, Felipe H. |
| author_facet | Altman, Aaron R. da Jornada, Felipe H. |
| contents | Photocatalytic reactions often exhibit fast kinetics and high product selectivity, qualities which are desirable but difficult to achieve simultaneously in thermally driven processes. However, photo-driven mechanisms are poorly understood owing to the difficulty in realistically modeling catalysts in optically excited states. Here we apply many-body perturbation theory (MBPT) calculations to gain insight into these mechanisms by studying a prototypical photocatalytic reaction, proton desorption from a rutile TiO${}_2$ (110) surface. Our calculations reveal a qualitatively different desorption process upon photoexcitation, with an over 50% reduction in the desorption energy and the emergence of an energy barrier. We rationalize these findings with a generalizable model based on Fano theory and explain the surprising increase of excitonic effects as the proton detaches from the surface. Our model also yields a connection between how the alignment of relevant ionization potentials affects the shape of the excited-state potential energy surface. These results cannot be qualitatively captured by typical constrained density-functional theory and highlight how contemporary first-principles MBPT calculations can be applied to design photocatalytic reactions. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2503_03136 |
| institution | arXiv |
| publishDate | 2025 |
| record_format | arxiv |
| spellingShingle | Ab Initio Mechanisms and Design Principles for Photodesorption from TiO${}_2$ Altman, Aaron R. da Jornada, Felipe H. Computational Physics Chemical Physics Photocatalytic reactions often exhibit fast kinetics and high product selectivity, qualities which are desirable but difficult to achieve simultaneously in thermally driven processes. However, photo-driven mechanisms are poorly understood owing to the difficulty in realistically modeling catalysts in optically excited states. Here we apply many-body perturbation theory (MBPT) calculations to gain insight into these mechanisms by studying a prototypical photocatalytic reaction, proton desorption from a rutile TiO${}_2$ (110) surface. Our calculations reveal a qualitatively different desorption process upon photoexcitation, with an over 50% reduction in the desorption energy and the emergence of an energy barrier. We rationalize these findings with a generalizable model based on Fano theory and explain the surprising increase of excitonic effects as the proton detaches from the surface. Our model also yields a connection between how the alignment of relevant ionization potentials affects the shape of the excited-state potential energy surface. These results cannot be qualitatively captured by typical constrained density-functional theory and highlight how contemporary first-principles MBPT calculations can be applied to design photocatalytic reactions. |
| title | Ab Initio Mechanisms and Design Principles for Photodesorption from TiO${}_2$ |
| topic | Computational Physics Chemical Physics |
| url | https://arxiv.org/abs/2503.03136 |