Towards Accurate Mixed Quantum Classical Simulations of Vibrational Polaritonic Chemistry
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arXiv
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| Format: | Preprint |
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2025
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| _version_ | 1866912223331352576 |
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| author | Hasyim, Muhammad R. Mandal, Arkajit Reichman, David R. |
| author_facet | Hasyim, Muhammad R. Mandal, Arkajit Reichman, David R. |
| contents | Interest in vibrational polaritonic chemistry, where ground-state chemical kinetics are modified via confined optical modes in a cavity, has surged in recent years. Although models have been developed to understand cavity-modified reactions, fully quantum mechanical simulations remain out of reach for the collective regime that involves many molecules, a critical aspect of the phenomenon. Mixed quantum-classical (MQC) simulations offer a scalable alternative, but their accuracy requires testing and potential improvements even in the single-molecule limit. In this work, we take this step by first introducing the mapping approach to surface hopping (MASH) to address the limitations of traditional MQC methods. Second, we incorporate a quantum treatment of the cavity mode, moving beyond the classical approximations often employed in previous studies. Results for a single-molecule model of vibrational polaritonic chemistry show that combining MASH with a quantum cavity mode yields the most accurate rates. However, this scheme may produce different long-time population dynamics at zero coupling depending on whether the cavity mode is quantized; a problem known as size-inconsistency in MASH. We address this problem proposing the $ε$-MASH approach, which forbids hopping between states with negligible nonadiabatic couplings (NACs). Combining MASH with a quantum cavity mode thus provides a promising approach for scalable and accurate MQC simulations in the collective regime. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2502_04570 |
| institution | arXiv |
| publishDate | 2025 |
| record_format | arxiv |
| spellingShingle | Towards Accurate Mixed Quantum Classical Simulations of Vibrational Polaritonic Chemistry Hasyim, Muhammad R. Mandal, Arkajit Reichman, David R. Quantum Physics Other Condensed Matter Chemical Physics Interest in vibrational polaritonic chemistry, where ground-state chemical kinetics are modified via confined optical modes in a cavity, has surged in recent years. Although models have been developed to understand cavity-modified reactions, fully quantum mechanical simulations remain out of reach for the collective regime that involves many molecules, a critical aspect of the phenomenon. Mixed quantum-classical (MQC) simulations offer a scalable alternative, but their accuracy requires testing and potential improvements even in the single-molecule limit. In this work, we take this step by first introducing the mapping approach to surface hopping (MASH) to address the limitations of traditional MQC methods. Second, we incorporate a quantum treatment of the cavity mode, moving beyond the classical approximations often employed in previous studies. Results for a single-molecule model of vibrational polaritonic chemistry show that combining MASH with a quantum cavity mode yields the most accurate rates. However, this scheme may produce different long-time population dynamics at zero coupling depending on whether the cavity mode is quantized; a problem known as size-inconsistency in MASH. We address this problem proposing the $ε$-MASH approach, which forbids hopping between states with negligible nonadiabatic couplings (NACs). Combining MASH with a quantum cavity mode thus provides a promising approach for scalable and accurate MQC simulations in the collective regime. |
| title | Towards Accurate Mixed Quantum Classical Simulations of Vibrational Polaritonic Chemistry |
| topic | Quantum Physics Other Condensed Matter Chemical Physics |
| url | https://arxiv.org/abs/2502.04570 |