Conditional Born-Oppenheimer Dynamics: Quantum Dynamics Simulations for the Model Porphine

Journal Of Physical Chemistry Letters 6, 1529 - 1535 (2015)

Conditional Born-Oppenheimer Dynamics: Quantum Dynamics Simulations for the Model Porphine

Guillermo Albareda,Josep Maria Bofill,Ivano Tavernelli,Fermin Huarte-Larrañaga,Francesc Illas, Angel Rubio

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 non-unitarily 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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This work has been supported by Spanish MINECO through research grants CTQ2011-22505, CTQ2012-30751, CTQ2013-41307, and FIS2013-46159-C3-1-P, by Generalitat de Catalunya grants 2014SGR97, 2014SGR-0139, 2014SGR25 and XRQTC, and by Grupos Consolidados UPV/EHU del Gobierno Vasco (IT578-13). GA acknowledges additional financial support from the Beatriu de Pin´os Program through Project No. 2010BP-A00069,FI acknowledges additional financial support through the 2009 ICREA Academia Award for Excellence in University Research, and AR acknowledges additional financial support from the European Research Council Advanced Grant DYNamo (ERC-2010- AdG-267374), the European Community FP7 project CRONOS (Grant number 280879-2) and COST Actions CM1204 (XLIC) and MP1306 (EUSpec).

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