Simulating Molecular Single Vibronic Level Fluorescence Spectra with ab initio Hagedorn Wavepacket Dynamics

Abstract

We present a practical, ab initio time-dependent method using Hagedorn wavepackets to efficiently simulate single vibronic level (SVL) fluorescence spectra of polyatomic molecules from arbitrary initial vibrational levels. We apply the method to compute SVL spectra of anthracene by performing wavepacket dynamics on a 66-dimensional harmonic potential energy surface constructed from density functional theory calculations. The Hagedorn approach captures both mode distortion (frequency changes) and mode mixing (Duschinsky rotation) within the harmonic approximation. We not only reproduce the previously reported simulation results for singly excited $12^1$ and ${\overline{11}}^1$ levels, but are also able to compute SVL spectra from multiply excited levels in good agreement with experiments. Notably, all spectra were obtained from the same wavepacket trajectory without any additional propagation beyond what is required for the emission spectrum from the ground vibrational level of the electronically excited state.

36 pages, 6 figures; Supporting Information: 10 pages, 5 figures

References in corpus (20)

• Computing quantum dynamics in the semiclassical regime
• On-the-fly ab initio semiclassical dynamics: Identifying degrees of freedom essential for emission spectra of oligothiophenes
• On-the-fly ab initio semiclassical evaluation of absorption spectra of polyatomic molecules beyond the Condon approximation
• Exponentially Accurate Semiclassical Dynamics: Propagation, Localization, Ehrenfest Times, Scattering and More General States
• Single-Hessian thawed Gaussian approximation: The missing rung on the ladder
• Semiclassical Approach to Photophysics Beyond Kasha's Rule and Vibronic Spectroscopy Beyond the Condon Approximation. The Case of Azulene
• On-the-fly ab initio semiclassical evaluation of vibronic spectra at finite temperature
• Vibrationally resolved electronic spectra including vibrational pre-excitation: Theory and application to VIPER spectroscopy
• Finite-temperature, anharmonicity, and Duschinsky effects on the two-dimensional electronic spectra from ab initio thermo-field Gaussian wavepacket dynamics
• On-the-fly ab initio semiclassical evaluation of third-order response functions for two-dimensional electronic spectroscopy
• On-the-fly ab initio three thawed Gaussians approximation: A semiclassical approach to Herzberg-Teller spectra
• Family of Gaussian wavepacket dynamics methods from the perspective of a nonlinear Schrödinger equation
• Internal Conversion Rates from the Extended Thawed Gaussian Approximation: Theory and Validation
• Exponentially Accurate Semiclassical Tunneling Wave Functions in One Dimension
• Symplectic Semiclassical Wave Packet Dynamics II: Non-Gaussian States
• Isotope effects in the electronic spectra of ammonia from ab initio semiclassical dynamics
• Prediction of Fluorescence Quantum Yields using the Extended Thawed Gaussian Approximation
• Single vibronic level fluorescence spectra from Hagedorn wavepacket dynamics
• On Hagedorn wavepackets associated with different Gaussians
• On-the-Fly Ab Initio Hagedorn Wavepacket Dynamics: Single Vibronic Level Fluorescence Spectra of Difluorocarbene