Non-Markovian Effects in Quantum Rate Calculations of Hydrogen Diffusion with Electronic Friction
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arXiv
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| Autores principales: | , |
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| Formato: | Preprint |
| Publicado: |
2024
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| _version_ | 1866909634064809984 |
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| author | Trenins, George Rossi, Mariana |
| author_facet | Trenins, George Rossi, Mariana |
| contents | We address the challenge of incorporating non-Markovian electronic friction effects in quantum-mechanical approximations of dynamical observables. A generalized Langevin equation (GLE) is formulated for ring-polymer molecular dynamics (RPMD) rate calculations, which combines electronic friction with a description of nuclear quantum effects (NQEs) for adsorbates on metal surfaces. An efficient propagation algorithm is introduced that captures both the spatial dependence of friction strength and non-Markovian frictional memory. This framework is applied to a model of hydrogen diffusing on Cu(111) derived from ab initio density functional theory (DFT) calculations, revealing significant alterations in rate constants and tunnelling crossover temperatures due to non-Markovian effects. Our findings explain why previous classical molecular dynamics simulations with Markovian friction showed unexpectedly good agreement with experiment, highlighting the critical role of non-Markovian effects in first-principles atomistic simulations. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2412_15014 |
| institution | arXiv |
| publishDate | 2024 |
| record_format | arxiv |
| spellingShingle | Non-Markovian Effects in Quantum Rate Calculations of Hydrogen Diffusion with Electronic Friction Trenins, George Rossi, Mariana Materials Science Chemical Physics We address the challenge of incorporating non-Markovian electronic friction effects in quantum-mechanical approximations of dynamical observables. A generalized Langevin equation (GLE) is formulated for ring-polymer molecular dynamics (RPMD) rate calculations, which combines electronic friction with a description of nuclear quantum effects (NQEs) for adsorbates on metal surfaces. An efficient propagation algorithm is introduced that captures both the spatial dependence of friction strength and non-Markovian frictional memory. This framework is applied to a model of hydrogen diffusing on Cu(111) derived from ab initio density functional theory (DFT) calculations, revealing significant alterations in rate constants and tunnelling crossover temperatures due to non-Markovian effects. Our findings explain why previous classical molecular dynamics simulations with Markovian friction showed unexpectedly good agreement with experiment, highlighting the critical role of non-Markovian effects in first-principles atomistic simulations. |
| title | Non-Markovian Effects in Quantum Rate Calculations of Hydrogen Diffusion with Electronic Friction |
| topic | Materials Science Chemical Physics |
| url | https://arxiv.org/abs/2412.15014 |