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

• URL: http://arxiv.org/abs/2403.00702v4
• Date: Thu, 27 Mar 2025 23:38:45 GMT
• Title: Simulating Molecular Single Vibronic Level Fluorescence Spectra with ab initio Hagedorn Wavepacket Dynamics
• Authors: Zhan Tong Zhang, Jiří J. L. Vaníček,
• Abstract summary: We present a practical, ab initio time-dependent method using Hagedorn wavepackets to efficiently simulate single vibronic level (SVL) fluorescence spectra of polyatomic molecules.<n>We apply the method to compute SVL spectra of anthracene by performing wavepacket dynamics on a 66-dimensional harmonic potential energy surface.
• Score: 0.0
• License: http://arxiv.org/licenses/nonexclusive-distrib/1.0/
• 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 and 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.

Related papers

• On-the-Fly Ab Initio Hagedorn Wavepacket Dynamics: Single Vibronic Level Fluorescence Spectra of Difluorocarbene [0.0]
  Hagedorn wavepackets have been used with local harmonic approximation to partially capture the anharmonic effects on single vibronic level (SVL) spectra in model potentials. We combine local harmonic Hagedorn wavepacket dynamics with on-the-fly ab initio dynamics. We show that, whereas global harmonic models are inadequate for CF$, spectra computed with the on-the-fly local harmonic Hagedorn wavepacket dynamics agree well with experimental data, especially for low initial excitations.
  arXiv  Detail & Related papers  (2024-09-03T13:04:44Z)
• Capturing anharmonic effects in single vibronic level fluorescence spectra using local harmonic Hagedorn wavepacket dynamics [0.0]
  We combine the Hagedorn approach to spectroscopy with the local harmonic approximation of the potential. We show that the local harmonic approach yields more accurate results than global harmonic approximations.
  arXiv  Detail & Related papers  (2024-08-21T21:01:59Z)
• Single vibronic level fluorescence spectra from Hagedorn wavepacket dynamics [0.0]
  We develop an efficient algorithm to compute the overlaps between two Hagedorn wavepackets. We study the effects of displacement, distortion (squeezing), and Duschinsky rotation on SVL spectra.
  arXiv  Detail & Related papers  (2024-03-01T14:58:07Z)
• Ab-Initio Vibro-Polaritonic Spectra in Strongly Coupled Cavity-Molecule Systems [0.0]
  We present an ab-initio methodology, based on the cavity Born-Oppenheimer Hartree-Fock ansatz, to calculate vibro-polaritonic IR spectra. Our semi-classical approach, validated against full quantum simulations, reproduces key features of the vibro-polaritonic spectra.
  arXiv  Detail & Related papers  (2023-10-03T08:16:21Z)
• Vibrational strong coupling in liquid water from cavity molecular dynamics [0.0]
  We show that our simulated cavity spectra can be reproduced to graphical accuracy with a harmonic model. We conclude that cavity molecular dynamics cannot provide any more insight into the effect of vibrational strong coupling on the absorption spectrum.
  arXiv  Detail & Related papers  (2023-05-04T10:33:14Z)
• Quantum emulation of the transient dynamics in the multistate Landau-Zener model [50.591267188664666]
  We study the transient dynamics in the multistate Landau-Zener model as a function of the Landau-Zener velocity. Our experiments pave the way for more complex simulations with qubits coupled to an engineered bosonic mode spectrum.
  arXiv  Detail & Related papers  (2022-11-26T15:04:11Z)
• Quantum-enhanced absorption spectroscopy with bright squeezed frequency combs [91.3755431537592]
  We propose a strategy combining the advantages of frequency modulation spectroscopy with the reduced noise properties accessible by squeezing the probe state. A homodyne detection scheme allows the simultaneous measurement of the absorption at multiple frequencies. We predict a significant enhancement of the signal-to-noise ratio that scales exponentially with the squeezing factor.
  arXiv  Detail & Related papers  (2022-09-30T17:57:05Z)
• Real-Space, Real-Time Approach to Quantum-Electrodynamical Time-Dependent Density Functional Theory [55.41644538483948]
  The equations are solved by time propagating the wave function on a tensor product of a Fock-space and real-space grid. Examples include the coupling strength and light frequency dependence of the energies, wave functions, optical absorption spectra, and Rabi splitting magnitudes in cavities.
  arXiv  Detail & Related papers  (2022-09-01T18:49:51Z)
• Calculating non-linear response functions for multi-dimensional electronic spectroscopy using dyadic non-Markovian quantum state diffusion [68.8204255655161]
  We present a methodology for simulating multi-dimensional electronic spectra of molecular aggregates with coupling electronic excitation to a structured environment. A crucial aspect of our approach is that we propagate the NMQSD equation in a doubled system Hilbert space but with the same noise.
  arXiv  Detail & Related papers  (2022-07-06T15:30:38Z)
• Unsupervised Spectral Unmixing For Telluric Correction Using A Neural Network Autoencoder [58.720142291102135]
  We present a neural network autoencoder approach for extracting a telluric transmission spectrum from a large set of high-precision observed solar spectra from the HARPS-N radial velocity spectrograph.
  arXiv  Detail & Related papers  (2021-11-17T12:54:48Z)
• Simulation of absorption spectra of molecular aggregates: a Hierarchy of Stochastic Pure States approach [68.8204255655161]
  hierarchy of pure states (HOPS) provides a formally exact solution based on local, trajectories. Exploiting the localization of HOPS for the simulation of absorption spectra in large aggregares requires a formulation in terms of normalized trajectories.
  arXiv  Detail & Related papers  (2021-11-01T16:59:54Z)
• Fano Resonances in Quantum Transport with Vibrations [50.591267188664666]
  Quantum mechanical scattering continuum states coupled to a scatterer with a discrete spectrum gives rise to Fano resonances. We consider scatterers that possess internal vibrational degrees of freedom in addition to discrete states.
  arXiv  Detail & Related papers  (2021-08-07T12:13:59Z)
• Visualizing spinon Fermi surfaces with time-dependent spectroscopy [62.997667081978825]
  We propose applying time-dependent photo-emission spectroscopy, an established tool in solid state systems, in cold atom quantum simulators. We show in exact diagonalization simulations of the one-dimensional $t-J$ model that the spinons start to populate previously unoccupied states in an effective band structure. The dependence of the spectral function on the time after the pump pulse reveals collective interactions among spinons.
  arXiv  Detail & Related papers  (2021-05-27T18:00:02Z)
• Machine Learning for Vibrational Spectroscopy via Divide-and-Conquer Semiclassical Initial Value Representation Molecular Dynamics with Application to N-Methylacetamide [56.515978031364064]
  A machine learning algorithm for partitioning the nuclear vibrational space into subspaces is introduced. The subdivision criterion is based on Liouville's theorem, i.e. best preservation of the unitary of the reduced dimensionality Jacobian determinant. The algorithm is applied to the divide-and-conquer semiclassical calculation of the power spectrum of 12-atom trans-N-Methylacetamide.
  arXiv  Detail & Related papers  (2021-01-11T14:47:33Z)

This list is automatically generated from the titles and abstracts of the papers in this site.

This site does not guarantee the quality of this site (including all information) and is not responsible for any consequences.