Effective temperature representation of quantum delocalization effects on the dynamics of NO(A2Σ+←X2Π+) photoexcitation in Ne matrices

文献信息

发布日期 2009-04-28
DOI 10.1039/B819355J
影响因子 3.676
作者

L. García-Reyes, J. Rubayo-Soneira


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摘要

The energetics of the optical excitation of the lowest Rydberg state of a nitric oxide molecule embedded in a neon matrix and the subsequent rearrangement of the solid host are investigated by classical molecular dynamics simulations. Quantum delocalization effects are incorporated through an effective temperature. The relevance of the inclusion of the anharmonicity of crystal site oscillations in the calculation of the effective temperature is evaluated. We show that representing zero point vibrations beyond the harmonic approximation improves the correspondence between the results of molecular dynamics simulations and pump–probe experiments performed on this system. We explored both the steady state spectroscopy and the relaxation dynamics of the doped matrix in this improved representation. The analysis of the Fourier components of particle density reveals that the system simulated within the quantum thermal harmonic correction does not fulfill the translational symmetry of the host crystal.

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来源期刊

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
自引率: 10.3%
年发文量: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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