Charge Migration Manifests as Attosecond Solitons in Conjugated Organic Molecules

Abstract

Charge migration is the electronic response that immediately follows localized ionization or excitation in a molecule, before the nuclei have time to move. It typically unfolds on sub-femtosecond time scales and most often corresponds to dynamics far from equilibrium, involving multi-electron interactions in a complex chemical environment. While charge migration has been documented experimentally and theoretically in multiple organic and inorganic compounds, the general mechanism that regulates it remains unsettled. In this work we use tools from nonlinear dynamics to analyze charge migration that takes place along the backbone of conjugated hydrocarbons, which we simulate using time-dependent density functional theory. In this electron-density framework we show that charge migration modes emerge as attosecond solitons and demonstrate the same type of solitary-wave dynamics in both simplified model systems and full three-dimensional molecular simulations. We show that these attosecond-soliton modes result from a balance between dispersion and nonlinear effects tied to time-dependent multi-electron interactions.%Our soliton-mode mechanism, and the nonlinear tools we use to analyze it, pave the way for understanding migration dynamics in a broad range of organic molecules.%For instance, we demonstrate the opportunities for chemically steering charge migration via molecular functionalization, which can alter both the initially localized electron perturbation and its subsequent time evolution.

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Cited by in corpus (12)

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• The role of symmetric vibrational modes in the dehoherence of correlation-driven charge migration
• Characterizing Particle-Like Charge Migration Dynamics with High-Harmonic Sideband Spectroscopy
• All-Electron, Density Functional-Based Method for Angle-Resolved Tunneling Ionization in the Adiabatic Regime
• The Exact Exchange-Correlation Potential in Time-Dependent Density Functional Theory: Choreographing Electrons with Steps and Peaks
• Tracking Charge Migration with Frequency-Matched Strobo-Spectroscopy
• Attosecond imaging of photo-induced dynamics in molecules using time-resolved photoelectron momentum microscopy
• A Laboratory Frame Density Matrix for Ultrafast Quantum Molecular Dynamics
• Size effect in correlation-driven charge migration in correlation bands of alkyne chains
• Simulating real-time molecular electron dynamics efficiently using the time-dependent density matrix renormalization group
• QMol-grid: A MATLAB package for quantum-mechanical simulations in atomic and molecular systems
• Hamiltonian formulation and symplectic split-operator schemes for time-dependent density-functional-theory equations of electron dynamics in molecules