A partially linearized spin-mapping approach for simulating nonlinear optical spectra

Abstract

We present a partially linearized method based on spin mapping for computing both linear and nonlinear optical spectra. As observables are obtained from ensembles of classical trajectories, the approach can be applied to the large condensed-phase systems that undergo photosynthetic light-harvesting processes. In particular, the recently derived spin-PLDM method has been shown to exhibit superior accuracy in computing population dynamics compared to other related classical-trajectory methods. Such a method should also be ideally suited to describing the quantum coherences generated by interaction with light. We demonstrate that this is indeed the case by calculating the nonlinear optical response functions relevant for the pump--probe and 2D photon-echo spectra for a Frenkel biexciton model and the Fenna--Matthews--Olsen light-harvesting complex. One especially desirable feature of our approach is that the full spectrum can be decomposed into its constituent components associated with the various Liouville-space pathways, offering a greater insight beyond what can be directly obtained from experiment.

24 pages, 13 figures

References in corpus (8)

• Perspective: Numerically "exact" approach to open quantum dynamics: The hierarchical equations of motion (HEOM)
• Generalized spin mapping for quantum-classical dynamics
• Coherent State Mapping Ring-Polymer Molecular Dynamics for Non-Adiabatic quantum propagations
• Linear and nonlinear spectroscopy from quantum master equations
• Efficient construction of generalized master equation memory kernels for multi-state systems from nonadiabatic quantum-classical dynamics
• Path integral approach to the Wigner representation of canonical density operators for discrete systems coupled to harmonic baths
• Generalized Discrete Truncated Wigner Approximation for Nonadiabtic Quantum-Classical Dynamics
• A bosonic perspective on the classical mapping of fermionic quantum dynamics

Cited by in corpus (11)

• A mapping approach to surface hopping
• Seeking a quantum advantage with trapped-ion quantum simulations of condensed-phase chemical dynamics
• Quasiclassical approaches to the generalized quantum master equation
• A simple improved low temperature correction for the hierarchical equations of motion
• On detailed balance in nonadiabatic dynamics: From spin spheres to equilibrium ellipsoids
• Efficient formulation of multitime generalized quantum master equations: Taming the cost of simulating 2D spectra
• Which Algorithm Best Propagates the Meyer-Miller-Stock-Thoss Mapping Hamiltonian for Non-Adiabatic Dynamics?
• Generalized quantum master equations can improve the accuracy of semiclassical predictions of multitime correlation functions
• Two-dimensional electronic spectra from trajectory-based dynamics: pure-state Ehrenfest, spin-mapping, and mean classical path approaches
• Machine learning meets $\mathfrak{su}(n)$ Lie algebra: Enhancing quantum dynamics learning with exact trace conservation
• Toward Quantum-Aware Machine Learning: Improved Prediction of Quantum Dissipative Dynamics via Complex Valued Neural Networks