标题： 激发态动力学中绝热表示的移动粗略绝热替代方案 显示英文标题

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

摘要： 在实时量子动力学中电子表象的选择至关重要。绝热表象具有吸引力，因为绝热态可以从量子化学软件包中轻松获得。然后，核波包在高斯函数基组上展开，这些函数沿着轨迹移动以探索势能面，并通过绝热量的局部展开近似势能。然而，当涉及锥形交叉时，绝热表象存在严重局限性：对角布居-奥本海默校正（DBOCs）不可积分，并且除非有模型可用，否则无法考虑几何相位效应对核波包的影响。为了解决这些问题，提出了移动粗粒度绝热（MCA）表象，并在波包绕过锥形交叉的低能动力学中成功测试了它。我们评估了MCA表象在通过锥形交叉发生非绝热跃迁的情况下的表现。首先，我们表明在绝热表象中使用高斯基组确实表现出上述问题，特别是强调了是否可以正规化DBOC项的可能性。然后，我们证明MCA确实能够正确模拟非绝热跃迁。这些测试是在双(亚甲基)金刚烷阳离子和丁三烯阳离子的线性振动耦合模型上进行的。 显示英文摘要

摘要： 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.