Semiclassical Approach to Photophysics Beyond Kasha's Rule and Vibronic Spectroscopy Beyond the Condon Approximation. The Case of Azulene

• URL: http://arxiv.org/abs/2001.08414v2
• Date: Mon, 23 Mar 2020 22:33:19 GMT
• Title: Semiclassical Approach to Photophysics Beyond Kasha's Rule and Vibronic Spectroscopy Beyond the Condon Approximation. The Case of Azulene
• Authors: Antonio Prlj, Tomislav Begu\v{s}i\'c, Zhan Tong Zhang, George Cameron Fish, Marius Wehrle, Tom\'a\v{s} Zimmermann, Seonghoon Choi, Julien Roulet, Jacques-Edouard Moser, Ji\v{r}\'i Van\'i\v{c}ek
• Abstract summary: We study the photophysics and spectroscopy of azulene and other non-conventional molecules. We develop a systematic, general, and efficient computational approach combining semiclassical dynamics of nuclei with ab initio electronic structure. We find that accuracy of the evaluated spectra requires the treatment of anharmonicity, Herzberg--Teller, and mode-mixing effects.
• Score: 0.0
• License: http://arxiv.org/licenses/nonexclusive-distrib/1.0/
• Abstract: Azulene is a prototypical molecule with an anomalous fluorescence from the second excited electronic state, thus violating Kasha's rule, and with an emission spectrum that cannot be understood within the Condon approximation. To better understand photophysics and spectroscopy of azulene and other non-conventional molecules, we develop a systematic, general, and efficient computational approach combining semiclassical dynamics of nuclei with ab initio electronic structure. First, to analyze the nonadiabatic effects, we complement the standard population dynamics by a rigorous measure of adiabaticity, estimated with the multiple-surface dephasing representation. Second, we propose a new semiclassical method for simulating non-Condon spectra, which combines the extended thawed Gaussian approximation with the efficient single-Hessian approach. S$_{1} \leftarrow$ S$_0$ and S$_{2} \leftarrow$ S$_0$ absorption and S$_{2} \rightarrow$ S$_0$ emission spectra of azulene, recorded in a new set of experiments, agree very well with our calculations. We find that accuracy of the evaluated spectra requires the treatment of anharmonicity, Herzberg--Teller, and mode-mixing effects.

Related papers

• Ab initio simulation of single vibronic level fluorescence spectra of anthracene using Hagedorn wavepackets [0.0]
  Single vibronic level (SVL) fluorescence spectroscopy contributes to the understanding of molecular vibrational structures and relaxation processes. Here, we present a practical method for computing SVL fluorescence spectra of polyatomic molecules from arbitrary initial vibrational levels.
  arXiv  Detail & Related papers  (2024-03-01T17:39:42Z)
• 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)
• Photoinduced prethermal order parameter dynamics in the two-dimensional large-$N$ Hubbard-Heisenberg model [77.34726150561087]
  We study the microscopic dynamics of competing ordered phases in a two-dimensional correlated electron model. We simulate the light-induced transition between two competing phases.
  arXiv  Detail & Related papers  (2022-05-13T13:13:31Z)
• Generalization of the Tavis-Cummings model for multi-level anharmonic systems: insights on the second excitation manifold [0.0]
  This work contrasts predictions from the Tavis-Cummings (TC) model, in which the material is a collection of two-level systems. We simplify the brute-force diagonalization of a gigantic $N2times N2$ Hamiltonian. We find resonant conditions between bipolaritons and anharmonic transitions where two-photon absorption can be enhanced.
  arXiv  Detail & Related papers  (2022-02-03T06:33:42Z)
• Applicability of the thawed Gaussian wavepacket dynamics to the calculation of vibronic spectra of molecules with double-well potential energy surfaces [0.0]
  We show that a semiclassical wavepacket approach is more robust and to provide more accurate spectra than the conventional harmonic approximation. The method is efficient and requires only a single classical ab initio molecular dynamics trajectory.
  arXiv  Detail & Related papers  (2022-01-14T20:30:41Z)
• 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)
• 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)
• On-the-fly ab initio semiclassical evaluation of third-order response functions for two-dimensional electronic spectroscopy [0.0]
  We use the single-trajectory semiclassical thawed Gaussian approximation to evaluate two-dimensional electronic spectra. We find that in this molecule, the anharmonicity effects are weak, whereas the Duschinsky rotation and the changes in the mode frequencies must be included in accurate simulations.
  arXiv  Detail & Related papers  (2020-10-06T21:29:11Z)
• On-the-fly ab initio semiclassical evaluation of vibronic spectra at finite temperature [0.0]
  ab initio extended thawed Gaussian approximation used to compute vibrationally resolved spectra at zero temperature. New approach allows for a clear distinction among finite-temperature, anharmonicity, and Herzberg-Teller effects on spectra.
  arXiv  Detail & Related papers  (2020-05-18T22:54:10Z)

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.