Improved population operators for multi-state nonadiabatic dynamics with the mixed quantum-classical mapping approach.,Faraday Discussions

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Improved population operators for multi-state nonadiabatic dynamics with the mixed quantum-classical mapping approach.
Faraday Discussions ( IF 3.3 ) Pub Date : 2019-12-16 , DOI: 10.1039/c9fd00050j
Maximilian A C Saller ₁ , Aaron Kelly , Jeremy O Richardson

Affiliation

The mapping approach addresses the mismatch between the continuous nuclear phase space and discrete electronic states by creating an extended, fully continuous phase space using a set of harmonic oscillators to encode the populations and coherences of the electronic states. Existing quasiclassical dynamics methods based on mapping, such as the linearised semiclassical initial value representation (LSC-IVR) and Poisson bracket mapping equation (PBME) approaches, have been shown to fail in predicting the correct relaxation of electronic-state populations following an initial excitation. Here we generalise our recently published modification to the standard quasiclassical approximation for simulating quantum correlation functions. We show that the electronic-state population operator in any system can be exactly rewritten as a sum of a traceless operator and the identity operator. We show that by treating the latter at a quantum level instead of using the mapping approach, the accuracy of traditional quasiclassical dynamics methods can be drastically improved, without changes to their underlying equations of motion. We demonstrate this approach for the seven-state Frenkel-exciton model of the Fenna-Matthews-Olson light harvesting complex, showing that our modification significantly improves the accuracy of traditional mapping approaches when compared to numerically exact quantum results.

中文翻译：

使用混合量子经典映射方法改进了多态非绝热动力学的种群算子。

映射方法通过使用一组谐波振荡器创建一个扩展的，完全连续的相空间来编码电子态的总体和相干性，从而解决了连续核相空间与离散电子态之间的不匹配问题。现有的基于映射的准经典动力学方法（例如线性化的半经典初始值表示（LSC-IVR）和泊松括号映射方程（PBME）方法）无法预测初始激发后电子态总体的正确弛豫。在这里，我们将对最近发布的标准准经典近似的修改进行概括，以模拟量子相关函数。我们表明，任何系统中的电子状态人口算子都可以精确地重写为无痕算子和身份算子的总和。我们表明，通过在量子水平上处理后者而不是使用映射方法，可以大大提高传统的准经典动力学方法的准确性，而无需更改其基本的运动方程式。我们为Fenna-Matthews-Olson光收集复合体的七态Frenkel-激子模型证明了这种方法，表明与数值精确的量子结果相比，我们的修改显着提高了传统映射方法的准确性。传统的准经典动力学方法的准确性可以大大提高，而无需改变其基本的运动方程。我们为Fenna-Matthews-Olson光收集复合体的七态Frenkel-激子模型证明了这种方法，表明与数值精确的量子结果相比，我们的修改显着提高了传统映射方法的准确性。传统的准经典动力学方法的准确性可以大大提高，而无需改变其基本的运动方程。我们为Fenna-Matthews-Olson光收集复合体的七态Frenkel-激子模型证明了这种方法，表明与数值精确的量子结果相比，我们的修改显着提高了传统映射方法的准确性。

更新日期：2019-12-17

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