使用塌缩为块的分子动力学模拟穿过锥形交叉级联的过程
Simulating Passage through a Cascade of Conical Intersections with Collapse-to-a-Block Molecular Dynamics
AI总结：
本文评估了TAB分子动力学方法及其变体（TAB-w和TAB-DMS）在二维锥形交叉级联模型中的性能，发现其能准确描述动力学过程，且变体在减少误差方面表现优异。
摘要：
最近引入了带有塌缩为块（TAB）的Ehrenfest分子动力学方法，以允许在多个电子态上进行精确的非绝热动力学模拟。先前的基准测试工作已证明该方法在模拟一维解析模型动力学时具有极高的准确性，但非绝热动力学通常涉及锥形交叉，这在本质上是二维的。在本报告中，我们评估了TAB在密集电子态流形中的锥形交叉级联二维模型上的性能。我们考虑了TAB的几种变体，包括基于相干性呈高斯衰减而非指数衰减假设的TAB-w，以及结合了基于近似本征态的高效塌缩过程的TAB-DMS。通过与数值精确的量子动力学模拟进行比较，发现所有TAB变体都能对穿过锥形交叉级联的动力学过程提供合适的描述。研究发现，TAB-w方法对布居数动力学的描述比原始TAB方法更为准确，在所有情况下最终的绝对布居数误差$\leq$0.013。即使仅计算四个近似本征态，使用近似本征态也仅引入了极小的额外误差（在所有模型中绝对布居数误差$\leq$0.018）。
英文摘要：
The Ehrenfest with collapse-to-a-block (TAB) molecular dynamics approach was recently introduced to allow accurate simulation of nonadiabatic dynamics on many electronic states. Previous benchmarking work has demonstrated it to be highly accurate for modeling dynamics in one-dimensional analytical models, but nonadiabatic dynamics often involves conical intersections, which are inherently two-dimensional. In this report, we assess the performance of TAB on two-dimensional models of cascades of conical intersections in dense manifolds of states. Several variants of TAB are considered, including TAB-w, which is based on the assumption of a Gaussian rather than exponential decay of the coherence, and TAB-DMS, which incorporates an efficient collapse procedure based on approximate eigenstates. Upon comparison to numerically exact quantum dynamics simulations, it is found that all TAB variants provide a suitable description of the dynamical passage through a cascade of conical intersections. The TAB-w approach is found to provide a somewhat more accurate description of population dynamics than the original TAB method, with final absolute population errors $\leq$0.013 in all cases. Even when only four approximate eigenstates are computed, the use of approximate eigenstates was found to introduce minimal additional error (absolute population error $\leq$0.018 in all models).
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