论文标题

激发态动力学中绝热表示的移动原油绝热替代品

The moving crude adiabatic alternative to the adiabatic representation in excited state dynamics

论文作者

Maskri, Rosa, Joubert-Doriol, Loïc

论文摘要

在直播量子动力学中的电子表示的选择至关重要。由于绝热状态可以从量子化学包装中获得,因此绝热表示有吸引力。然后以高斯函数的基础扩展核波袋,该功能遵循轨迹探索势能表面并使用绝热量的局部扩张来近似电势。然而,当涉及圆锥形交集时,绝热表示受到严重的限制:对角线 - 邻苯二聚符校正(DBOC)是不可整合的,并且除非有模型,否则对核波袋的几何相位影响无法解释。为了避免这些困难,提出了移动的绝热(MCA)表示形式,并在波袋裙子裙式圆锥形相交的低能动力学中成功进行了测试。在通过圆锥形交集进行非绝热过渡的情况下,我们评估了MCA表示。首先,我们表明,在绝热表示中使用高斯基础确实表现出了上述困难,并特别强调了将DBOC术语正规化的可能性。然后,我们表明MCA确实能够正确地对非绝热过渡进行建模。对BIS(亚甲基)金氨酰基阳离子和丁烷阳离子的线性振动耦合模型进行了测试。

The choice of the electronic representation in on-the-fly quantum dynamics is crucial. The adiabatic representation is appealing since adiabatic states are readily available from quantum chemistry packages. The nuclear wavepackets are then expanded in a basis of Gaussian functions, which follow trajectories to explore the potential energy surfaces and approximate the potential using a local expansion of the adiabatic quantities. Nevertheless, the adiabatic representation is plagued with severe limitations when conical intersections are involved: the diagonal Born-Oppenheimer corrections (DBOCs) are non-integrable, and the geometric phase effect on the nuclear wavepackets cannot be accounted for unless a model is available. To circumvent these difficulties, the moving crude adiabatic (MCA) representation was proposed and successfully tested in low energy dynamics where the wavepacket skirts the conical intersection. We assess the MCA representation in the case of non-adiabatic transitions through conical intersections. First, we show that using a Gaussian basis in the adiabatic representation indeed exhibits the aforementioned difficulties with a special emphasis on the possibility to regularize the DBOC terms. Then, we show that MCA is indeed able to properly model non-adiabatic transitions. Tests are done on linear vibronic coupling models for the bis(methylene) adamantyl cation and the butatriene cation.

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