Analyzing Grid-Based Direct Quantum Molecular Dynamics Using Non-Linear Dimensionality Reduction
Grid-based schemes for simulating quantum dynamics, such as the multi-configuration time-dependent Hartree (MCTDH) method, provide highly accurate predictions of the coupled nuclear and electronic dynamics in molecular systems. Such approaches provide a multi-dimensional, time-dependent view of the...
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| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2021-12-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/26/24/7418 |
| _version_ | 1797502212491968512 |
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| author | Gareth W. Richings Scott Habershon |
| author_facet | Gareth W. Richings Scott Habershon |
| author_sort | Gareth W. Richings |
| collection | DOAJ |
| description | Grid-based schemes for simulating quantum dynamics, such as the multi-configuration time-dependent Hartree (MCTDH) method, provide highly accurate predictions of the coupled nuclear and electronic dynamics in molecular systems. Such approaches provide a multi-dimensional, time-dependent view of the system wavefunction represented on a coordinate grid; in the case of non-adiabatic simulations, additional information about the state populations adds a further layer of complexity. As such, wavepacket motion on potential energy surfaces which couple many nuclear and electronic degrees-of-freedom can be extremely challenging to analyse in order to extract physical insight beyond the usual expectation-value picture. Here, we show that non-linear dimensionality reduction (NLDR) methods, notably diffusion maps, can be adapted to extract information from grid-based wavefunction dynamics simulations, providing insight into key nuclear motions which explain the observed dynamics. This approach is demonstrated for 2-D and 9-D models of proton transfer in salicylaldimine, as well as 8-D and full 12-D simulations of <i>cis</i>-<i>trans</i> isomerization in ethene; these simulations demonstrate how NLDR can provide alternative views of wavefunction dynamics, and also highlight future developments. |
| first_indexed | 2024-03-10T03:29:44Z |
| format | Article |
| id | doaj.art-dd44851c68084ed1be5bdf481d93b2ba |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-10T03:29:44Z |
| publishDate | 2021-12-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-dd44851c68084ed1be5bdf481d93b2ba2023-11-23T09:43:44ZengMDPI AGMolecules1420-30492021-12-012624741810.3390/molecules26247418Analyzing Grid-Based Direct Quantum Molecular Dynamics Using Non-Linear Dimensionality ReductionGareth W. Richings0Scott Habershon1Department of Chemistry, University of Warwick, Coventry CV4 7AL, UKDepartment of Chemistry, University of Warwick, Coventry CV4 7AL, UKGrid-based schemes for simulating quantum dynamics, such as the multi-configuration time-dependent Hartree (MCTDH) method, provide highly accurate predictions of the coupled nuclear and electronic dynamics in molecular systems. Such approaches provide a multi-dimensional, time-dependent view of the system wavefunction represented on a coordinate grid; in the case of non-adiabatic simulations, additional information about the state populations adds a further layer of complexity. As such, wavepacket motion on potential energy surfaces which couple many nuclear and electronic degrees-of-freedom can be extremely challenging to analyse in order to extract physical insight beyond the usual expectation-value picture. Here, we show that non-linear dimensionality reduction (NLDR) methods, notably diffusion maps, can be adapted to extract information from grid-based wavefunction dynamics simulations, providing insight into key nuclear motions which explain the observed dynamics. This approach is demonstrated for 2-D and 9-D models of proton transfer in salicylaldimine, as well as 8-D and full 12-D simulations of <i>cis</i>-<i>trans</i> isomerization in ethene; these simulations demonstrate how NLDR can provide alternative views of wavefunction dynamics, and also highlight future developments.https://www.mdpi.com/1420-3049/26/24/7418quantum dynamicsMCTDHdiffusion maps |
| spellingShingle | Gareth W. Richings Scott Habershon Analyzing Grid-Based Direct Quantum Molecular Dynamics Using Non-Linear Dimensionality Reduction Molecules quantum dynamics MCTDH diffusion maps |
| title | Analyzing Grid-Based Direct Quantum Molecular Dynamics Using Non-Linear Dimensionality Reduction |
| title_full | Analyzing Grid-Based Direct Quantum Molecular Dynamics Using Non-Linear Dimensionality Reduction |
| title_fullStr | Analyzing Grid-Based Direct Quantum Molecular Dynamics Using Non-Linear Dimensionality Reduction |
| title_full_unstemmed | Analyzing Grid-Based Direct Quantum Molecular Dynamics Using Non-Linear Dimensionality Reduction |
| title_short | Analyzing Grid-Based Direct Quantum Molecular Dynamics Using Non-Linear Dimensionality Reduction |
| title_sort | analyzing grid based direct quantum molecular dynamics using non linear dimensionality reduction |
| topic | quantum dynamics MCTDH diffusion maps |
| url | https://www.mdpi.com/1420-3049/26/24/7418 |
| work_keys_str_mv | AT garethwrichings analyzinggridbaseddirectquantummoleculardynamicsusingnonlineardimensionalityreduction AT scotthabershon analyzinggridbaseddirectquantummoleculardynamicsusingnonlineardimensionalityreduction |