Combined Surface-Hopping, Dyson Orbital, and B-Spline Approach for the Computation of Time-Resolved Photoelectron Spectroscopy Signals: The Internal Conversion in Pyrazine

Piteša, Tomislav; Sapunar, Marin; Ponzi, Aurora; Gelin, Maxim F.; Došlić, Nađa; Domcke, Wolfgang; Decleva, Piero

doi:10.1021/acs.jctc.1c00396

Cited by 19 publications

(29 citation statements)

References 75 publications

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“…The transient population of the dark A u state in the photophysics of pyrazine has become a controversially discussed topic in the recent literature. ,− While Suzuki and co-workers could not find evidence for the intermediate population of the A u state, − Leone and co-workers reported detection of population in the A u state with a time delay of 200 fs . A recent computational simulation of the TRPES of pyrazine confirmed that the A u population indeed cannot be clearly distinguished from the B 3u population in TRPES . According to quantum dynamics calculations for an ab initio based three-state nine-mode model of pyrazine as well as full-dimensional ab initio quasiclassical SH simulations for pyrazine, the (diabatic) B 3u and A u states are comparably populated already after 50 fs (Figure b).…”

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confidence: 93%

“…Experimentally, the photodynamics of pyrazine was studied by Suzuki and co-workers with femtosecond time-resolved photoelectron spectroscopy (TRPES) in the UV − and very recently by Leone and co-workers with femtosecond X-ray absorption spectroscopy . The transient population of the dark A u state in the photophysics of pyrazine has become a controversially discussed topic in the recent literature. ,− While Suzuki and co-workers could not find evidence for the intermediate population of the A u state, − Leone and co-workers reported detection of population in the A u state with a time delay of 200 fs . A recent computational simulation of the TRPES of pyrazine confirmed that the A u population indeed cannot be clearly distinguished from the B 3u population in TRPES .…”

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confidence: 99%

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Ab Initio Quasiclassical Simulation of Femtosecond Time-Resolved Two-Dimensional Electronic Spectra of Pyrazine

Huang

Xie

Došlić

et al. 2021

J. Phys. Chem. Lett.

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Two-dimensional (2D) electronic spectroscopy is a powerful nonlinear technique which provides spectroscopic information on two frequency axes as well as dynamical information as a function of the so-called waiting time. Herein, an ab initio theoretical framework for the simulation of electronic 2D spectra has been developed. The method is based on the classical approximation to the doorway−window representation of three-pulse photon-echo signals and the description of nuclear motion by classical trajectories. Nonadiabatic effects are taken into account by a trajectory surface-hopping algorithm. 2D electronic spectra were simulated with ab initio on-the-fly trajectory calculations using the ADC(2) electronic-structure method for the pyrazine molecule, which is a benchmark system for ultrafast radiationless decay through conical intersections. It is demonstrated that 2D spectroscopy with subfemtosecond UV pulses can provide unprecedented detailed information on the ultrafast photodynamics of polyatomic molecules.

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confidence: 93%

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confidence: 99%

Ab Initio Quasiclassical Simulation of Femtosecond Time-Resolved Two-Dimensional Electronic Spectra of Pyrazine

Huang

Xie

Došlić

et al. 2021

J. Phys. Chem. Lett.

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“…In this calculation, all atoms are described by a double zeta polarized basis (DZP) and the LB94 functional has been used to describe exchange and correlation effects [ 41 ]. The choice of this functional is well supported by a significant number of accurate photoionization studies performed over the years [ 42 , 43 , 44 ]. The parameters used to calculate bound and continuum orbitals expressed in the B-spline LCAO basis have been chosen to reach convergence with the lowest computational cost.…”

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confidence: 99%

Discrimination of Excited States of Acetylacetone through Theoretical Molecular-Frame Photoelectron Angular Distributions

et al. 2022

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Photoelectron angular distribution (PAD) in the laboratory frame for randomly oriented molecules is typically described by a single anisotropy parameter, the so-called asymmetry parameter. However, especially from a theoretical perspective, it is more natural to consider molecular photoionization by using a molecular frame. The molecular frame PADs (MFPADs) may be used to extract information about the electronic structure of the system studied. In the last decade, significant experimental efforts have been directed to MFPAD measurements. MFPADs are highly characterizing signatures of the final ionic states. In particular, they are very sensitive to the nature of the final state, which is embodied in the corresponding Dyson orbital. In our previous work on acetylacetone, a prototype system for studying intra-molecular hydrogen bond interactions, we followed the dynamics of the excited states involved in the photoexcitation–deexcitation process of this molecule. It remains to be explored the possibility of discriminating between different excited states through the MFPAD profiles. The calculation of MFPADs to differentiate excited states can pave the way to the possibility of a clear discrimination for all the cases where the recognition of excited states is otherwise intricate.

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“…In addition to improving the diabatic-adiabatic transformation in vMCG calculations, a possible approach for this comparison would be the computation of the diabatic populations in TSH simulations. While ways of doing this have been proposed [41,54], a systematic implementation is not yet available.…”

Section: Direct-dynamics: Butatriene and Cyclohexadienementioning

confidence: 99%

Mixed-quantum-classical or fully-quantized dynamics? A unified code to compare methods

Coonjobeeharry

Spinlove

Sanz-Sanz

et al. 2022

Phil. Trans. R. Soc. A.

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Three methods for non-adiabatic dynamics are compared to highlight their capabilities. Multi-configurational time-dependent Hartree is a full grid-based solution to the time-dependent Schrödinger equation, variational multi-configurational Gaussian (vMCG) uses a less flexible but unrestricted Gaussian wavepacket basis, and trajectory surface hopping (TSH) replaces the nuclear wavepacket with a swarm of classical trajectories. Calculations with all methods using a model Hamiltonian were performed. The vMCG and TSH were also then run in a direct dynamics mode, with the potential energy surfaces calculated on-the-fly using quantum chemistry calculations. All dynamics calculations used the Q uantics package, with the TSH calculations using a new interface to a surface hopping code. A novel approach to calculate adiabatic populations from grid-based quantum dynamics using a time-dependent discrete variable representation is presented, allowing a proper comparison of methods. This article is part of the theme issue ‘Chemistry without the Born–Oppenheimer approximation’.

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Combined Surface-Hopping, Dyson Orbital, and B-Spline Approach for the Computation of Time-Resolved Photoelectron Spectroscopy Signals: The Internal Conversion in Pyrazine

Cited by 19 publications

References 75 publications

Ab Initio Quasiclassical Simulation of Femtosecond Time-Resolved Two-Dimensional Electronic Spectra of Pyrazine

Ab Initio Quasiclassical Simulation of Femtosecond Time-Resolved Two-Dimensional Electronic Spectra of Pyrazine

Discrimination of Excited States of Acetylacetone through Theoretical Molecular-Frame Photoelectron Angular Distributions

Mixed-quantum-classical or fully-quantized dynamics? A unified code to compare methods

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