Nonadiabatic Derivative Couplings Calculated Using Information of Potential Energy Surfaces without Wavefunctions : Ab Initio and Machine Learning Implementations
In this work, we implemented an approximate algorithm for calculating nonadiabatic coupling matrix elements (NACMEs) of a polyatomic system with ab initio methods and machine learning (ML) models. Utilizing this algorithm, one can calculate NACMEs using only the information of potential energy surfaces (PESs), i.e., energies, and gradients as well as Hessian matrix elements. We used a realistic system, namely CH2NH, to compare NACMEs calculated by this approximate PES-based algorithm and the accurate wavefunction-based algorithm. Our results show that this approximate PES-based algorithm can give very accurate results comparable to the wavefunction-based algorithm except at energetically degenerate points, i.e., conical intersections. We also tested a machine learning (ML)-trained model with this approximate PES-based algorithm, which also supplied similarly accurate NACMEs but more efficiently. The advantage of this PES-based algorithm is its significant potential to combine with electronic structure methods that do not implement wavefunction-based algorithms, low-scaling energy-based fragment methods, etc., and in particular efficient ML models, to compute NACMEs. The present work could encourage further research on nonadiabatic processes of large systems simulated by ab initio nonadiabatic dynamics simulation methods in which NACMEs are always required.
| Medienart: |
E-Artikel |
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| Erscheinungsjahr: |
2023 |
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| Erschienen: |
2023 |
| Enthalten in: |
Zur Gesamtaufnahme - volume:28 |
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| Enthalten in: |
Molecules (Basel, Switzerland) - 28(2023), 10 vom: 21. Mai |
| Sprache: |
Englisch |
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| Beteiligte Personen: |
Chen, Wen-Kai [VerfasserIn] |
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| Links: |
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| Themen: |
Excited states |
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| Anmerkungen: |
Date Completed 28.05.2023 Date Revised 30.05.2023 published: Electronic Citation Status PubMed-not-MEDLINE |
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| doi: |
10.3390/molecules28104222 |
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| funding: |
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| Förderinstitution / Projekttitel: |
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| PPN (Katalog-ID): |
NLM357441893 |
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| 100 | 1 | |a Chen, Wen-Kai |e verfasserin |4 aut | |
| 245 | 1 | 0 | |a Nonadiabatic Derivative Couplings Calculated Using Information of Potential Energy Surfaces without Wavefunctions |b Ab Initio and Machine Learning Implementations |
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| 500 | |a Date Revised 30.05.2023 | ||
| 500 | |a published: Electronic | ||
| 500 | |a Citation Status PubMed-not-MEDLINE | ||
| 520 | |a In this work, we implemented an approximate algorithm for calculating nonadiabatic coupling matrix elements (NACMEs) of a polyatomic system with ab initio methods and machine learning (ML) models. Utilizing this algorithm, one can calculate NACMEs using only the information of potential energy surfaces (PESs), i.e., energies, and gradients as well as Hessian matrix elements. We used a realistic system, namely CH2NH, to compare NACMEs calculated by this approximate PES-based algorithm and the accurate wavefunction-based algorithm. Our results show that this approximate PES-based algorithm can give very accurate results comparable to the wavefunction-based algorithm except at energetically degenerate points, i.e., conical intersections. We also tested a machine learning (ML)-trained model with this approximate PES-based algorithm, which also supplied similarly accurate NACMEs but more efficiently. The advantage of this PES-based algorithm is its significant potential to combine with electronic structure methods that do not implement wavefunction-based algorithms, low-scaling energy-based fragment methods, etc., and in particular efficient ML models, to compute NACMEs. The present work could encourage further research on nonadiabatic processes of large systems simulated by ab initio nonadiabatic dynamics simulation methods in which NACMEs are always required | ||
| 650 | 4 | |a Journal Article | |
| 650 | 4 | |a excited states | |
| 650 | 4 | |a machine learning | |
| 650 | 4 | |a nonadiabatic couplings | |
| 700 | 1 | |a Wang, Sheng-Rui |e verfasserin |4 aut | |
| 700 | 1 | |a Liu, Xiang-Yang |e verfasserin |4 aut | |
| 700 | 1 | |a Fang, Wei-Hai |e verfasserin |4 aut | |
| 700 | 1 | |a Cui, Ganglong |e verfasserin |4 aut | |
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