Albareda Guillermo, Bofill Josep Maria, Tavernelli Ivano, Huarte-Larrañaga Fermin, Illas Francesc, Rubio Angel
†Institut de Química Teòrica i Computacional, Universitat de Barcelona, Barcelona 08028, Spain.
‡Departament de Química Física, Universitat de Barcelona, Barcelona 08028, Spain.
J Phys Chem Lett. 2015 May 7;6(9):1529-35. doi: 10.1021/acs.jpclett.5b00422. Epub 2015 Apr 10.
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.
我们报告了一种新的理论方法，用于在波函数和基于轨迹的方法之间求解绝热量子分子动力学。在3N维的玻恩-奥本海默势能超曲面上移动的N体核波函数的演化，被重写为在3维势能面上非幺正演化的单核波函数，该势能面参数化地依赖于一组一般定义轨迹的构型。该方案是精确的，并且与基于轨迹的统计技术一起，可以用于规避多体量（例如波函数和势能面）的计算和存储，这些多体量的大小随核自由度数量呈指数增长。作为概念验证，我们给出了一个二维模型卟啉的数值模拟，其中量子力学诱导了从协同双质子转移到顺序双质子转移（以及反向）的转变。
