Oloyede Ponmile, Mil'nikov Gennady, Nakamura Hiroki
Department of Functional Molecular Science, The Graduate University for Advanced Studies, Myodaiji, Okazaki 444-8585, Japan.
J Chem Phys. 2006 Apr 14;124(14):144110. doi: 10.1063/1.2187978.
We present a generalized formulation of the trajectory surface hopping method applicable to a general multidimensional system. The method is based on the Zhu-Nakamura theory of a nonadiabatic transition and therefore includes the treatment of classically forbidden hops. The method uses a generalized recipe for the conservation of angular momentum after forbidden hops and an approximation for determining a nonadiabatic transition direction which is crucial when the coupling vector is unavailable. This method also eliminates the need for a rigorous location of the seam surface, thereby ensuring its applicability to a wide class of chemical systems. In a test calculation, we implement the method for the DH(2) (+) system, and it shows a remarkable agreement with the previous results of C. Zhu, H. Kamisaka, and H. Nakamura, [J. Chem. Phys. 116, 3234 (2002)]. We then apply it to a diatomic-in-molecule model system with a conical intersection, and the results compare well with exact quantum calculations. The successful application to the conical intersection system confirms the possibility of directly extending the present method to an arbitrary potential of general topology.
我们提出了一种适用于一般多维系统的轨迹表面跳跃方法的广义公式。该方法基于朱 - 中村非绝热跃迁理论，因此包括对经典禁戒跳跃的处理。该方法采用了一种广义规则来处理禁戒跳跃后的角动量守恒，并采用一种近似方法来确定非绝热跃迁方向，当耦合矢量不可用时，这一点至关重要。该方法还无需精确确定接缝表面的位置，从而确保其适用于广泛的化学系统。在一个测试计算中，我们将该方法应用于DH(2)(+)系统，结果与C.朱、H.上坂和H.中村之前的结果[《化学物理杂志》116, 3234 (2002)]显示出显著的一致性。然后我们将其应用于具有锥形交叉点的分子内双原子模型系统，结果与精确的量子计算结果吻合良好。对锥形交叉点系统的成功应用证实了将本方法直接扩展到具有一般拓扑结构的任意势的可能性。
