Conditional Born-Oppenheimer dynamics: quantum dynamics simulations for the model porphine
We report a new theoretical approach to solve adiabatic quantum molecular dynamics halfway between wave function and trajectory-based methods. The evolution of a N- body nuclear wave function moving on a 3N-dimensional Born−Oppenheimer potential-energy hyper-surface is rewritten in terms of single-n...
| Autores: | , , , , , |
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| Formato: | artículo |
| Estado: | Versión aceptada para publicación |
| Fecha de publicación: | 2015 |
| País: | España |
| Recursos: | Varias* (Consorci de Biblioteques Universitáries de Catalunya, Centre de Serveis Científics i Acadèmics de Catalunya) |
| Repositorio: | Recercat. Dipósit de la Recerca de Catalunya |
| OAI Identifier: | oai:recercat.cat:2445/153918 |
| Acesso em linha: | https://hdl.handle.net/2445/153918 |
| Access Level: | acceso abierto |
| Palavra-chave: | Química física Química quàntica Dinàmica molecular Physical and theoretical chemistry Quantum chemistry Molecular dynamics |
| Resumo: | We report a new theoretical approach to solve adiabatic quantum molecular dynamics halfway between wave function and trajectory-based methods. The evolution of a N- body nuclear wave function moving on a 3N-dimensional Born−Oppenheimer potential-energy hyper-surface is rewritten in terms of single-nuclei wave functions evolving nonunitarily on a 3-dimensional potential-energy surface that depends parametrically on the configuration of an ensemble of generally defined trajectories. The scheme is exact and, together with the use of trajectory-based statistical techniques, can be exploited to circumvent the calculation and storage of many-body quantities (e.g., wave function and potential-energy surface) whose size scales exponentially with the number of nuclear degrees of freedom. As a proof of concept, we present numerical simulations of a 2-dimensional model porphine where switching from concerted to sequential double proton transfer (and back) is induced quantum mechanically |
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