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| Main Authors: | , , , |
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| Format: | Preprint |
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2024
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| Subjects: | |
| Online Access: | https://arxiv.org/abs/2401.11926 |
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| _version_ | 1866909204888944640 |
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| author | Woźniak, Aleksander P. Adamowicz, Ludwik Pedersen, Thomas Bondo Kvaal, Simen |
| author_facet | Woźniak, Aleksander P. Adamowicz, Ludwik Pedersen, Thomas Bondo Kvaal, Simen |
| contents | The assumptions underpinning the adiabatic Born-Oppenheimer (BO) approximation are broken for molecules interacting with attosecond laser pulses, which generate complicated coupled electronic-nuclear wavepackets that generally will have components of electronic and dissociation continua as well as bound-state contributions. The conceptually most straightforward way to overcome this challenge is to treat the electronic and nuclear degrees of freedom on equal quantum-mechanical footing by not invoking the BO approximation at all. Explicitly correlated Gaussian (ECG) basis functions have proved successful for non-BO calculations of stationary molecular states and energies, reproducing rovibrational absorption spectra with very high accuracy. In this paper, we present a proof-of-principle study of the ability of fully flexible ECGs (FFECGs) to capture the intricate electronic and rovibrational dynamics generated by short, high-intensity laser pulses. By fitting linear combinations of FFECGs to accurate wave function histories obtained on a large real-space grid for a regularized 2D model of the hydrogen atom and for the 2D Morse potential we demonstrate that FFECGs provide a very compact description of laser-driven electronic and rovibrational dynamics. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2401_11926 |
| institution | arXiv |
| publishDate | 2024 |
| record_format | arxiv |
| spellingShingle | Gaussians for Electronic and Rovibrational Quantum Dynamics Woźniak, Aleksander P. Adamowicz, Ludwik Pedersen, Thomas Bondo Kvaal, Simen Chemical Physics The assumptions underpinning the adiabatic Born-Oppenheimer (BO) approximation are broken for molecules interacting with attosecond laser pulses, which generate complicated coupled electronic-nuclear wavepackets that generally will have components of electronic and dissociation continua as well as bound-state contributions. The conceptually most straightforward way to overcome this challenge is to treat the electronic and nuclear degrees of freedom on equal quantum-mechanical footing by not invoking the BO approximation at all. Explicitly correlated Gaussian (ECG) basis functions have proved successful for non-BO calculations of stationary molecular states and energies, reproducing rovibrational absorption spectra with very high accuracy. In this paper, we present a proof-of-principle study of the ability of fully flexible ECGs (FFECGs) to capture the intricate electronic and rovibrational dynamics generated by short, high-intensity laser pulses. By fitting linear combinations of FFECGs to accurate wave function histories obtained on a large real-space grid for a regularized 2D model of the hydrogen atom and for the 2D Morse potential we demonstrate that FFECGs provide a very compact description of laser-driven electronic and rovibrational dynamics. |
| title | Gaussians for Electronic and Rovibrational Quantum Dynamics |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2401.11926 |