Intraband Exciton Transitions in Photosynthetic Complexes Revealed by Novel Five-Wave-Mixing Spectroscopy
Intraband Exciton Transitions in Photosynthetic Complexes Revealed by Novel Five-Wave-Mixing Spectroscopy
复制标题
新型五波混合光谱揭示光合复合物中的带内激子跃迁
DOI：
10.1021/acs.jctc.3c00919
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发表时间：
2024
影响因子：
5.5
通讯作者：
Mukamel, Shaul
中科院分区：
文献类型：
--
作者：
Kizmann, Matthias;Yadalam, Hari Kumar;Chernyak, Vladimir Y.;Mukamel, Shaul
利用非线性激子方程（NEE）计算了紫色细菌定向光系统II反应中心的χ（4）光学响应。这种方法将每个发色团作为一个非谐振子，并提供了一个直观的准粒子图片的相互作用激子的非线性光谱信号。它提供了一个计算功能强大的描述非线性光谱信号，避免完全对角化的总哈密顿量。推导了二阶和四阶非线性信号的表达式。NEE在过去已经成功地用于描述偶阶波混频。在这里，我们将它们扩展到破坏反转对称的聚集体。偶数阶双稳态需要引入永久偶极子，这允许直接探测激子的低频带内跃迁。
We calculate the χ(4)optical response of an oriented photosystem II reaction center of purple bacteria described by the Frenkel exciton model using nonlinear exciton equations (NEE). This approach treats each chromophore as an anharmonic oscillator and provides an intuitive quasiparticle picture of nonlinear spectroscopic signals of interacting excitons. It provides a computationally powerful description of nonlinear spectroscopic signals that avoids complete diagonalization of the total Hamiltonian. Expressions for the second- and the fourth-order nonlinear signals are derived. The NEE have been successfully employed in the past to describe even-order-wave-mixing. Here, we extend them to aggregates with broken inversion symmetries. Even-order susceptibilities require the introduction of permanent dipoles, which allow to directly probe low-frequency intraband transitions of excitons.