Timescales of N–H bond dissociation in pyrrole: a nonadiabatic dynamics study

2015 ◽  
Vol 17 (29) ◽  
pp. 19012-19020 ◽  
Author(s):  
Marin Sapunar ◽  
Aurora Ponzi ◽  
Sermsiri Chaiwongwattana ◽  
Momir Mališ ◽  
Antonio Prlj ◽  
...  
Keyword(s):  
Excitation Wavelength ◽  
Nonadiabatic Dynamics ◽  
Surface Hopping ◽  
Bond Dissociation ◽  
Dynamics Simulations

The excitation wavelength dependent photodynamics of pyrrole are investigated by surface-hopping nonadiabatic dynamics simulations. The results are explained in terms of correct Rydberg–valence interaction in the lowest B2 state.

scholarly journals Nonadiabatic Dynamics in Multidimensional Complex Potential Energy Surfaces

2020 ◽  
Author(s):  
Fábris Kossoski ◽  
Mario Barbatti
Keyword(s):  
Potential Energy ◽  
Potential Energy Surfaces ◽  
Electron Attachment ◽  
Complex Surface ◽  
Nonadiabatic Dynamics ◽  
Surface Hopping ◽  
Molecular Systems ◽  
Out Of Plane ◽  
Dynamics Simulations ◽  
Energy Surfaces

<p>Despite the continuous development of theoretical methodologies for describing nonadiabatic dynamics of molecular systems, there is a lack of approaches for processes where the norm of the wave function is not conserved, i.e., when an imaginary potential accounts for some irreversible decaying mechanism. Current approaches rely on building potential energy surfaces of reduced dimensionality, which is not optimal for more involving and realistic multidimensional problems. Here, we present a novel methodology for describing the dynamics of complex-valued molecular Hamiltonians, which is a generalisation of the trajectory surface hopping method. As a first application, the complex surface fewest switches surface hopping (CS-FSSH) method was employed to survey the relaxation mechanisms of the shape resonant anions of iodoethene. We have provided the first detailed and dynamical picture of the p*/s* mechanism of dissociative electron attachment in halogenated unsaturated compounds, which is believed to underlie electron-induced reactions of several molecules of interest. Electron capture into the p* orbital promotes C=C stretching and out-of-plane vibrations, followed by charge transfer from the double bond into the s* orbital at the C-I bond, and, finally, release of the iodine ion, all within only 15 fs. On-the-fly dynamics simulations of a vast class of processes can be envisioned with the CS-FSSH methodology, including autoionisation from transient anions, core-ionised and superexcited states, Auger and interatomic Coulombic decay, and time-dependent luminescence.</p>

scholarly journals Highly efficient surface hopping dynamics using a linear vibronic coupling model

2019 ◽  
Vol 21 (1) ◽  
pp. 57-69 ◽  
Author(s):  
Felix Plasser ◽  
Sandra Gómez ◽  
Maximilian F. S. J. Menger ◽  
Sebastian Mai ◽  
Leticia González
Keyword(s):  
Internal Conversion ◽  
Coupling Model ◽  
Vibronic Coupling ◽  
Intersystem Crossing ◽  
Nonadiabatic Dynamics ◽  
Surface Hopping ◽  
Highly Efficient ◽  
Dynamics Simulations

A highly efficient protocol for performing nonadiabatic dynamics simulations is implemented and applied to ultrafast internal conversion and intersystem crossing in various molecules.

scholarly journals Nonadiabatic dynamics simulations of singlet fission in 2,5-bis(fluorene-9-ylidene)-2,5-dihydrothiophene crystals

2019 ◽  
Vol 21 (2) ◽  
pp. 692-701 ◽  
Author(s):  
Meilani Wibowo ◽  
Maurizio Persico ◽  
Giovanni Granucci
Keyword(s):  
Quantum Yield ◽  
Nonadiabatic Dynamics ◽  
Singlet Fission ◽  
Surface Hopping ◽  
Dynamics Simulations

Singlet fission mechanism and quantum yield for a thienoquinodal compound from surface hopping simulations.

scholarly journals Excited-state intramolecular proton transfer to carbon atoms: nonadiabatic surface-hopping dynamics simulations

2015 ◽  
Vol 17 (15) ◽  
pp. 9687-9697 ◽  
Author(s):  
Shu-Hua Xia ◽  
Bin-Bin Xie ◽  
Qiu Fang ◽  
Ganglong Cui ◽  
Walter Thiel
Keyword(s):  
Electronic Structure ◽  
Excited State ◽  
Proton Transfer ◽  
Intramolecular Proton Transfer ◽  
Nonadiabatic Dynamics ◽  
Surface Hopping ◽  
Dynamics Simulations

The combined electronic structure computations and nonadiabatic dynamics simulations show that excited-state intramolecular proton transfer to carbon atoms can be ultrafast.

scholarly journals Nonadiabatic Dynamics in Multidimensional Complex Potential Energy Surfaces

2020 ◽  
Author(s):  
Fábris Kossoski ◽  
Mario Barbatti
Keyword(s):  
Potential Energy ◽  
Potential Energy Surfaces ◽  
Electron Attachment ◽  
Complex Surface ◽  
Nonadiabatic Dynamics ◽  
Surface Hopping ◽  
Molecular Systems ◽  
Out Of Plane ◽  
Dynamics Simulations ◽  
Energy Surfaces

<p>Despite the continuous development of theoretical methodologies for describing nonadiabatic dynamics of molecular systems, there is a lack of approaches for processes where the norm of the wave function is not conserved, i.e., when an imaginary potential accounts for some irreversible decaying mechanism. Current approaches rely on building potential energy surfaces of reduced dimensionality, which is not optimal for more involving and realistic multidimensional problems. Here, we present a novel methodology for describing the dynamics of complex-valued molecular Hamiltonians, which is a generalisation of the trajectory surface hopping method. As a first application, the complex surface fewest switches surface hopping (CS-FSSH) method was employed to survey the relaxation mechanisms of the shape resonant anions of iodoethene. We have provided the first detailed and dynamical picture of the π*/σ* mechanism of dissociative electron attachment in halogenated unsaturated compounds, which is believed to underlie electron-induced reactions of several molecules of interest. Electron capture into the π* orbital promotes C=C stretching and out-of-plane vibrations, followed by charge transfer from the double bond into the σ* orbital at the C-I bond, and, finally, release of the iodine ion, all within only 15 fs. On-the-fly dynamics simulations of a vast class of processes can be envisioned with the CS-FSSH methodology, including autoionisation from transient anions, core-ionised and superexcited states, Auger and interatomic Coulombic decay, and time-dependent luminescence.</p>

Chiral conversion and periodical decay in bridged-azobenzene photoisomerization: an ab initio on-the-fly nonadiabatic dynamics simulation

RSC Advances ◽  
2016 ◽  
Vol 6 (46) ◽  
pp. 39542-39552 ◽  
Author(s):  
Wanqing Gao ◽  
Le Yu ◽  
Xiaolei Zheng ◽  
Yibo Lei ◽  
Chaoyuan Zhu ◽  
...  
Keyword(s):  
Ab Initio ◽  
Dynamics Simulation ◽  
Nonadiabatic Dynamics ◽  
Surface Hopping ◽  
Dynamics Simulations

On-the-fly trajectory surface hopping dynamics simulations on the cis ↔ trans photoisomerization mechanisms of bridged-azobenzene upon S1 excitation at the CASSCF level.

scholarly journals Nonadiabatic Dynamics in Multidimensional Complex Potential Energy Surfaces

2020 ◽  
Author(s):  
Fábris Kossoski ◽  
Mario Barbatti
Keyword(s):  
Potential Energy ◽  
Potential Energy Surfaces ◽  
Electron Attachment ◽  
Complex Surface ◽  
Nonadiabatic Dynamics ◽  
Surface Hopping ◽  
Molecular Systems ◽  
Out Of Plane ◽  
Dynamics Simulations ◽  
Energy Surfaces

<p>Despite the continuous development of theoretical methodologies for describing nonadiabatic dynamics of molecular systems, there is a lack of approaches for processes where the norm of the wave function is not conserved, i.e., when an imaginary potential accounts for some irreversible decaying mechanism. Current approaches rely on building potential energy surfaces of reduced dimensionality, which is not optimal for more involving and realistic multidimensional problems. Here, we present a novel methodology for describing the dynamics of complex-valued molecular Hamiltonians, which is a generalisation of the trajectory surface hopping method. As a first application, the complex surface fewest switches surface hopping (CS-FSSH) method was employed to survey the relaxation mechanisms of the shape resonant anions of iodoethene. We have provided the first detailed and dynamical picture of the π*/σ* mechanism of dissociative electron attachment in halogenated unsaturated compounds, which is believed to underlie electron-induced reactions of several molecules of interest. Electron capture into the π* orbital promotes C=C stretching and out-of-plane vibrations, followed by charge transfer from the double bond into the σ* orbital at the C-I bond, and, finally, release of the iodine ion, all within only 15 fs. On-the-fly dynamics simulations of a vast class of processes can be envisioned with the CS-FSSH methodology, including autoionisation from transient anions, core-ionised and superexcited states, Auger and interatomic Coulombic decay, and time-dependent luminescence.</p>

scholarly journals Nonadiabatic dynamics with quantum nuclei: simulating charge transfer with ring polymer surface hopping

2020 ◽  
Vol 221 ◽  
pp. 501-525 ◽  
Author(s):  
Soumya Ghosh ◽  
Samuele Giannini ◽  
Kevin Lively ◽  
Jochen Blumberger
Keyword(s):  
Charge Transfer ◽  
Polymer Surface ◽  
Nonadiabatic Dynamics ◽  
Surface Hopping ◽  
Different Temperatures ◽  
Ring Polymer ◽  
Adiabatic Dynamics

Exploring effects of quantizing nuclei in non-adiabatic dynamics for simulating charge transfer in a dimer of “ethylene-like-molecules” at different temperatures.

scholarly journals X-ray transient absorption reveals the 1Au (nπ*) state of pyrazine in electronic relaxation

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Valeriu Scutelnic ◽  
Shota Tsuru ◽  
Mátyás Pápai ◽  
Zheyue Yang ◽  
Michael Epshtein ◽  
...  
Keyword(s):  
Electronic Excitation ◽  
Transient Absorption ◽  
Transient Absorption Spectroscopy ◽  
Electronic Relaxation ◽  
Nonadiabatic Dynamics ◽  
X Ray ◽  
Organic Chromophores ◽  
Dynamics Simulations ◽  
X Ray Absorption ◽  
Structure Calculations

AbstractElectronic relaxation in organic chromophores often proceeds via states not directly accessible by photoexcitation. We report on the photoinduced dynamics of pyrazine that involves such states, excited by a 267 nm laser and probed with X-ray transient absorption spectroscopy in a table-top setup. In addition to the previously characterized 1B2u (ππ*) (S2) and 1B3u (nπ*) (S1) states, the participation of the optically dark 1Au (nπ*) state is assigned by a combination of experimental X-ray core-to-valence spectroscopy, electronic structure calculations, nonadiabatic dynamics simulations, and X-ray spectral computations. Despite 1Au (nπ*) and 1B3u (nπ*) states having similar energies at relaxed geometry, their X-ray absorption spectra differ largely in transition energy and oscillator strength. The 1Au (nπ*) state is populated in 200 ± 50 femtoseconds after electronic excitation and plays a key role in the relaxation of pyrazine to the ground state.

Photophysics of Auramine-O: electronic structure calculations and nonadiabatic dynamics simulations

2016 ◽  
Vol 18 (1) ◽  
pp. 403-413 ◽  
Author(s):  
Bin-Bin Xie ◽  
Shu-Hua Xia ◽  
Xue-Ping Chang ◽  
Ganglong Cui
Keyword(s):  
Electronic Structure ◽  
Electronic Structure Calculations ◽  
Nonadiabatic Dynamics ◽  
Auramine O ◽  
Dynamics Simulations ◽  
Structure Calculations

Sequential vs. concerted S1 relaxation pathways.

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