Overlapping resonances in the control of intramolecular vibrational redistribution

Nonadiabatic Sunlight-harvesting

Experimental and theoretical evidence point out to the crucial role of specific resonant intramolecular vibrational modes in the interpretation of long-lived coherences observed in two-dimensional spectra of some natural and synthetic light harvesting complexes. For the natural situation of illumination by incoherent (sun)light, the relevance of these vibrations is analyzed here for light-harvesting vibronic prototype dimers. The detailed analysis of the density matrix dynamics reveals that the inclusion of the intramolecular vibrational modes reinforce up to one order of magnitude the exciton…

Calculations of Nonlinear Wave-Packet Interferometry Signals in the Pump-Probe Limit as Tests for Vibrational Control over Electronic Excitation Transfer

The preceding paper describes a strategy for externally influencing the course of short-time electronic excitation transfer (EET) in molecular dimers and observing the process by nonlinear wave-packet interferometry (nl-WPI). Within a sample of isotropically oriented dimers having a specified internal geometry, a vibrational mode internal to the acceptor chromophore can be preferentially driven by electronically nonresonant impulsive stimulated Raman (or resonant infrared) excitation with a short polarized control pulse. A subsequent electronically resonant polarized pump then preferentially e…

Electronic-vibrational resonance does not alter steady-state transport in natural light-harvesting systems

Oscillations in time-dependent 2D electronic spectra appear as evidence of quantum coherence in light-harvesting systems related to electronic-vibrational resonant interactions. Nature, however, takes place in a non-equilibrium steady-state, so the relevance of these arguments to the natural process is unclear. Here we examine the role of intramolecular vibrations in the non-equilibrium steady-state of photosynthetic dimers in the natural scenario of incoherent light excitation. It is found that vibrations resonant with the energy difference between exciton states do not increase the quantum y…

通过非共振激光脉冲诱导的极化率相互作用操控振动波包的最优控制

Optimal control for manipulating vibrational wave packets through polarizability interactions induced by non-resonant laser pulses

本文基于最优控制理论研究利用非共振激光脉冲诱导的极化率相互作用操控分子振动波包，针对I2的B态系统考察了选择性布居转移、波包整形和波包形变抑制三类目标，发现最优解为与振动动力学协同利用量子干涉的NR脉冲序列。

Vibration-assisted resonance in photosynthetic excitation energy transfer

Understanding how the effectiveness of natural photosynthetic energy harvesting systems arises from the interplay between quantum coherence and environmental noise represents a significant challenge for quantum theory. Recently it has begun to be appreciated that discrete molecular vibrational modes may play an important role in the dynamics of such systems. As an alternative to computationally demanding numerical approaches, we present a microscopic mechanism by which intramolecular vibrations contribute to the efficiency and directionality of energy transfer. Excited vibrational states creat…

相干非线性光学探针用于腔体修饰的振动模式混合：多维双量子相干与光子回声光谱

Coherent nonlinear optical probe for cavity-dressed vibrational mode mixing: Multidimensional double-quantum coherence and photon-echo spectroscopy

本研究提出两种多维光谱技术，用于监测腔体修饰振动激发，并揭示了耗散环境中振动模式的超快动态特性。

Femtosecond dynamics and laser control of charge transport in trans-polyacetylene

The induction of dc electronic transport in rigid and flexible trans-polyacetylene oligomers according to the $ω$ vs. $2ω$ coherent control scenario is investigated using a quantum-classical mean field approximation. The approach involves running a large ensemble of mixed quantum-classical trajectories under the influence of $ω+2ω$ laser fields, and choosing the initial conditions by sampling the ground-state Wigner distribution function for the nuclei. The vibronic couplings are shown to change the mean single-particle spectrum, introduce ultrafast decoherence, and enhance intramolecular vibr…

Manipulating the Dynamics of a Fermi Resonance with Light. A Direct Optimal Control Theory Approach

Direct optimal control theory for quantum dynamical problems presents itself as an interesting alternative to the traditional indirect optimal control. The method relies on the first discretize and then optimize paradigm, where a discretization of the dynamical equations leads to a nonlinear optimization problem. It has been applied successfully to the control of a bistable system where the wavepacket had been approximated by a parameterized Gaussian, leading to a semiclassical set of equations of motion (A. R. Ramos Ramos, O. Kühn, Front. Phys. 9 (2021) 615168). Motivated by these results, in…