Anharmonic spectral features via trajectory-based quantum dynamics: a perturbative analysis of the interplay between dynamics and sampling
| Autor: | Sara Bonella, Simon Huppert, Philippe Depondt, Thomas Plé, Fabio Finocchi |
|---|---|
| Přispěvatelé: | Institut des Nanosciences de Paris (INSP), Sorbonne Université (SU)-Centre National de la Recherche Scientifique (CNRS), Ecole Polytechnique Fédérale de Lausanne (EPFL) |
| Jazyk: | angličtina |
| Rok vydání: | 2021 |
| Předmět: |
high-pressure
Zero point energy Quantum dynamics molecular-dynamics water General Physics and Astronomy Zero-point energy rates formulation Perturbation theory Molecular dynamics 01 natural sciences Quantum statistical mechanics Edgeworth expansion 0103 physical sciences Initial value problem Statistical physics Matsubara dynamics Physical and Theoretical Chemistry 010306 general physics Quantum Fermi resonance Physics 010304 chemical physics Vibrational spectra Quantum effects time-correlation-functions multiple-scale analysis proton-transfer [CHIM.THEO]Chemical Sciences/Theoretical and/or physical chemistry Path integral formulation Semiclassical methods Perturbation theory (quantum mechanics) vibrational-energy relaxation mechanics Coherence (physics) |
| Zdroj: | Journal of Chemical Physics Journal of Chemical Physics, American Institute of Physics, 2021, 155 (10), pp.104108. ⟨10.1063/5.0056824⟩ |
| ISSN: | 0021-9606 1089-7690 |
| Popis: | The performance of different approximate algorithms for computing anharmonic features in vibrational spectra is analyzed and compared on model and more realistic systems that present relevant nuclear quantum effects. The methods considered combine approximate sampling of the quantum thermal distribution with classical time propagation and include Matsubara dynamics, path integral dynamics approaches, linearized initial value representation, and the recently introduced adaptive quantum thermal bath. A perturbative analysis of these different methods enables us to account for the observed numerical performance on prototypes for overtones and combination bands and to draw qualitatively correct trends for the numerical results obtained for Fermi resonances. Our results prove that the unequal performances of these approaches often derive from the method employed to sample initial conditions and not, as usually assumed, from the lack of coherence in the time propagation. Furthermore, as confirmed by the analysis reported in Benson and Althorpe, J. Chem. Phys. 130, 194510 (2021), we demonstrate, both via the perturbative approach and numerically, that path integral dynamics methods fail to reproduce the intensities of these anharmonic features and follow purely classical trends with respect to their temperature behavior. Finally, the remarkably accurate performance of the adaptive quantum thermal bath approach is documented and motivated. Published under an exclusive license by AIP Publishing. |
| Databáze: | OpenAIRE |
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