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-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.
†Institut de Química Teòrica i Computacional, Universitat de Barcelona, Barcelona 08028, Spain.|‡Departament de Química Física, Universitat de Barcelona, Barcelona 08028, Spain.
Guillermo
G
Albareda
†Institut de Química Teòrica i Computacional, Universitat de Barcelona, Barcelona 08028, Spain.|§Departament de Química Orgànica, Universitat de Barcelona, Barcelona 08028, Spain.
Josep Maria
JM
Bofill
∥IBM Research Zurich, Säumerstrasse 4, 8803 Rüschlikon, Switzerland.
Ivano
I
Tavernelli
†Institut de Química Teòrica i Computacional, Universitat de Barcelona, Barcelona 08028, Spain.|‡Departament de Química Física, Universitat de Barcelona, Barcelona 08028, Spain.
Fermin
F
Huarte-Larrañaga
†Institut de Química Teòrica i Computacional, Universitat de Barcelona, Barcelona 08028, Spain.|‡Departament de Química Física, Universitat de Barcelona, Barcelona 08028, Spain.
Francesc
F
Illas
⊥Max Planck Institute for the Structure and Dynamics of Matter, Luruper Chaussee 149, 22761 Hamburg, Germany.
Angel
A
Rubio
Ab-initio Molecular Dynamics; Born−Oppenheimer Approximation; Porphine; Quantum Dynamics; Quantum Effects; Quantum Trajectories