scholarly journals Nonadiabatic dynamics in multidimensional complex potential energy surfaces

2020 ◽  
Vol 11 (36) ◽  
pp. 9827-9835 ◽  
Author(s):  
Fábris Kossoski ◽  
Mario Barbatti
Keyword(s):  
Wave Function ◽  
Potential Energy ◽  
Complex Potential ◽  
Potential Energy Surfaces ◽  
Nonadiabatic Dynamics ◽  
Continuous Development ◽  
Surface Hopping ◽  
Multidimensional Complex ◽  
Function Norm ◽  
Energy Surfaces

Despite the continuous development of methods for describing nonadiabatic dynamics, there is a lack of multidimensional approaches for processes where the wave function norm is not conserved. A new surface hopping variant closes this knowledge gap.

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 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 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>

Nonadiabatic molecular dynamics simulation for the ultrafast photoisomerization of dMe-OMe-NAIP based on TDDFT on-the-fly potential energy surfaces

2021 ◽  
Vol 23 (9) ◽  
pp. 5236-5243
Author(s):  
Ying Hu ◽  
Chao Xu ◽  
Linfeng Ye ◽  
Feng Long Gu ◽  
Chaoyuan Zhu
Keyword(s):  
Molecular Dynamics ◽  
Molecular Dynamics Simulation ◽  
Potential Energy ◽  
Potential Energy Surfaces ◽  
Dynamics Simulation ◽  
Surface Hopping ◽  
Nonadiabatic Molecular Dynamics ◽  
Energy Surfaces

Global switching on-the-fly trajectory surface hopping molecular dynamics simulation was performed on the accurate TD-B3LYP/6-31G* potential energy surfaces for E-to-Z and Z-to-E photoisomerization of dMe-OMe-NAIP up to S1(ππ*) excitation.

Reduced-dimensional surface hopping with offline–online computations

2021 ◽  
Author(s):  
Zachary Morrow ◽  
Hyuk-Yong Kwon ◽  
Carl Tim Kelley ◽  
Elena Jakubikova
Keyword(s):  
Molecular Dynamics ◽  
Potential Energy ◽  
Molecular Dynamics Simulations ◽  
Potential Energy Surfaces ◽  
Energy Levels ◽  
Surface Hopping ◽  
Dynamics Simulations ◽  
Energy Surfaces ◽  
Nuclear Geometry ◽  
Dimensional Surface

Molecular dynamics simulations often classically evolve the nuclear geometry on adiabatic potential energy surfaces (PESs), punctuated by random hops between energy levels in regions of strong coupling, in an algorithm...

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