Department of Chemistry, University of Houston, Houston, Texas, USA; email:
Department of Physics and Center for Functional Materials, Wake Forest University, Winston-Salem, North Carolina, USA.
Annu Rev Phys Chem. 2023 Apr 24;74:467-492. doi: 10.1146/annurev-physchem-102822-100922. Epub 2023 Feb 28.
We review our recent quantum stochastic model for spectroscopic lineshapes in the presence of a coevolving and nonstationary background population of excitations. Starting from a field theory description for interacting bosonic excitons, we derive a reduced model whereby optical excitons are coupled to an incoherent background via scattering as mediated by their screened Coulomb coupling. The Heisenberg equations of motion for the optical excitons are then driven by an auxiliary stochastic population variable, which we take to be the solution of an Ornstein-Uhlenbeck process. Here, we present an overview of the theoretical techniques we have developed as applied to predicting coherent nonlinear spectroscopic signals. We show how direct (Coulomb) and exchange coupling to the bath give rise to distinct spectral signatures and discuss mathematical limits on inverting spectral signatures to extract the background density of states.
我们回顾了最近在共演和非稳态背景激发子群存在下的光谱线形状的量子随机模型。从相互作用玻色激子的场论描述出发,我们推导出一个简化模型,其中光学激子通过散射与非相干背景耦合,散射由它们的屏蔽库仑耦合介导。然后,光学激子的海森堡运动方程由一个辅助随机种群变量驱动,我们将其视为奥恩斯坦-乌伦贝克过程的解。在这里,我们概述了我们开发的理论技术,这些技术应用于预测相干非线性光谱信号。我们展示了直接(库仑)和与浴的交换耦合如何产生不同的光谱特征,并讨论了将光谱特征反转以提取背景态密度的数学限制。