The coupled-trajectory mixed quantum-classical method (CTMQC), derived from the exact factorization approach, has successfully predicted photo-chemical dynamics in a number of interesting molecules, capturing population transfer and decoherence from first principles. However, due to the approximations made, CTMQC does not guarantee energy conservation. We propose a modified algorithm, CTMQC-E, which redefines the integrated force in the coupled-trajectory term so to restore energy conservation, and demonstrate its accuracy on scattering in Tully's extended coupling region model and photoisomerization in a retinal chromophore model.
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http://dx.doi.org/10.1063/5.0149116 | DOI Listing |
J Chem Phys
January 2025
Department of Chemistry, School of Science, Westlake University, Hangzhou, Zhejiang 310024, China.
One key challenge in the study of nonadiabatic dynamics in open quantum systems is to balance computational efficiency and accuracy. Although Ehrenfest dynamics (ED) is computationally efficient and well-suited for large complex systems, ED often yields inaccurate results. To address these limitations, we improve the accuracy of the traditional ED by adding a random force (E + σ).
View Article and Find Full Text PDFJ Chem Phys
January 2025
Scuola Normale Superiore, Piazza dei Cavalieri 7, 56126 Pisa, Italy.
A multiscale quantum mechanical (QM)/classical approach is presented that is able to model the optical properties of complex nanostructures composed of a molecular system adsorbed on metal nanoparticles. The latter is described by a combined atomistic-continuum model, where the core is described using the implicit boundary element method (BEM) and the surface retains a fully atomistic picture and is treated employing the frequency-dependent fluctuating charge and fluctuating dipole (ωFQFμ) approach. The integrated QM/ωFQFμ-BEM model is numerically compared with state-of-the-art fully atomistic approaches, and the quality of the continuum/core partition is evaluated.
View Article and Find Full Text PDFJ Chem Phys
January 2025
Institute of Physics, University of Freiburg, Hermann-Herder-Strasse 3, 79104 Freiburg, Germany.
We explore the role of molecular vibrations in the chirality-induced spin selectivity (CISS) effect in the context of charge transport through a molecular nanojunction. We employ a mixed quantum-classical approach that combines Ehrenfest dynamics for molecular vibrations with the hierarchical equations of motion method for the electronic degrees of freedom. This approach treats the molecular vibrations in a nonequilibrium manner, which is crucial for the dynamics of molecular nanojunctions.
View Article and Find Full Text PDFJ Chem Phys
December 2024
Deep Space Exploration Laboratory/Department of Modern Mechanics, University of Science and Technology of China, Hefei 230026, People's Republic of China.
This paper performed a comprehensive study of the thermal nonequilibrium effects of CO/Ar mixtures with various degrees of N2 additions and probed the N2 relaxation behaviors via the CO rovibrational thermometry. The rovibrational temperature time histories of shock-heated CO/N2/Ar mixtures were measured via a laser-absorption technique, and the corresponding vibrational relaxation data were summarized at 1890-3490 K. The measured results were compared with predictions from the Schwartz-Slawsky-Herzfeld (SSH) formula and the state-to-state (StS) approach (treating CO and N2 as pseudo-species).
View Article and Find Full Text PDFChem Sci
January 2025
Faculty of Chemistry, Institute of Theoretical Chemistry, Universität Wien A-1090 Vienna Austria
Recent developments in quantum computing are highly promising, particularly in the realm of quantum chemistry. Due to the noisy nature of currently available quantum hardware, hybrid quantum-classical algorithms have emerged as a reliable option for near-term simulations. Mixed quantum-classical dynamics methods effectively capture nonadiabatic effects by integrating classical nuclear dynamics with quantum chemical computations of the electronic properties.
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