Quantum dissipative systems beyond the standard harmonic model: Features of linear absorption and dynamics
| العنوان: | Quantum dissipative systems beyond the standard harmonic model: Features of linear absorption and dynamics |
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| المؤلفون: | Arend G. Dijkstra, Luke D. Smith |
| المصدر: | The Journal of chemical physics. 151(16) |
| سنة النشر: | 2019 |
| مصطلحات موضوعية: | Population, FOS: Physical sciences, General Physics and Astronomy, Harmonic (mathematics), 010402 general chemistry, Curvature, 01 natural sciences, Schrödinger equation, symbols.namesake, Physics - Chemical Physics, 0103 physical sciences, Physics::Chemical Physics, Physical and Theoretical Chemistry, education, Harmonic oscillator, Morse potential, Chemical Physics (physics.chem-ph), Physics, Quantum Physics, education.field_of_study, 010304 chemical physics, Anharmonicity, 0104 chemical sciences, Classical mechanics, symbols, Dissipative system, Quantum Physics (quant-ph) |
| الوصف: | Current simulations of ultraviolet-visible absorption lineshapes, and dynamics of condensed phase systems, largely adopt a harmonic description to model vibrations. Often, this involves a model of displaced harmonic oscillators that have the same curvature. Although convenient, for many realistic molecular systems this approximation no longer suffices. We elucidate non-standard harmonic, and anharmonic effects, on linear absorption and dynamics using a stochastic Schr\"{o}dinger equation approach to account for the environment. Firstly, a harmonic oscillator model with ground and excited potentials that differ in curvature is utilised. Using this model, it is shown that curvature difference gives rise to an additional sub-structure in the vibronic progression of absorption spectra. This effect is explained, and subsequently quantified, via a derived expression for the Franck-Condon coefficients. Subsequently, anharmonic features in dissipative systems are studied, using a Morse potential, and parameters that correspond to the diatomic molecule $H_{2}$ for differing displacements and environment interaction. Lastly using a model potential, the population dynamics and absorption spectra for the stiff-stilbene photoswitch is presented and features are explained by a combination of curvature difference and anharmonicity in the form of potential energy barriers on the excited potential. Comment: 16 pages, 9 figures |
| وصف الملف: | application/pdf |
| تدمد: | 1089-7690 0021-9606 |
| URL الوصول: | https://explore.openaire.eu/search/publication?articleId=doi_dedup___::da788b4f83618b2094c4e11df9d30940 https://pubmed.ncbi.nlm.nih.gov/31675870 |
| حقوق: | OPEN |
| رقم الأكسشن: | edsair.doi.dedup.....da788b4f83618b2094c4e11df9d30940 |
| قاعدة البيانات: | OpenAIRE |
Find this article in full text from Scitation. | تدمد: | 10897690 00219606 |
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