scholarly journals Ultrafast dynamics with the exact factorization

Author(s):  
Federica Agostini ◽  
E. K. U. Gross

Abstract The exact factorization of the time-dependent electron–nuclear wavefunction has been employed successfully in the field of quantum molecular dynamics simulations for interpreting and simulating light-induced ultrafast processes. In this work, we summarize the major developments leading to the formulation of a trajectory-based approach, derived from the exact factorization equations, capable of dealing with nonadiabatic electronic processes, and including spin-orbit coupling and the non-perturbative effect of an external time-dependent field. This trajectory-based quantum-classical approach has been dubbed coupled-trajectory mixed quantum-classical (CT-MQC) algorithm, whose performance is tested here to study the photo-dissociation dynamics of IBr. Graphic abstract

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Min Li ◽  
Ming Zhang ◽  
Oriol Vendrell ◽  
Zhenning Guo ◽  
Qianru Zhu ◽  
...  

AbstractThe Jahn-Teller effect is an essential mechanism of spontaneous symmetry breaking in molecular and solid state systems, and has far-reaching consequences in many fields. Up to now, to directly image the onset of Jahn-Teller symmetry breaking remains unreached. Here we employ ultrafast ion-coincidence Coulomb explosion imaging with sub-10 fs resolution and unambiguously image the ultrafast dynamics of Jahn-Teller deformations of $${{\rm{CH}}}_{4}^{+}$$ CH 4 + cation in symmetry space. It is unraveled that the Jahn-Teller deformation from C3v to C2v geometries takes a characteristic time of 20 ± 7 fs for this system. Classical and quantum molecular dynamics simulations agree well with the measurement, and reveal dynamics for the build-up of the C2v structure involving complex revival process of multiple vibrational pathways of the $${{\rm{CH}}}_{4}^{+}$$ CH 4 + cation.


2020 ◽  
Author(s):  
Min Li ◽  
Ming Zhang ◽  
Oriol Vendrell ◽  
Zhenning Guo ◽  
Qianru Zhu ◽  
...  

Abstract The Jahn-Teller effect is an essential mechanism of spontaneous symmetry breaking in molecular and solid state systems, and has far-reaching consequences in many fields. Up to now, to direct image the onset of Jahn-Teller symmetry breaking remains unreached. Employing ultrafast ion-coincidence Coulomb explosion imaging with sub-10 fs resolution, we unambiguously imaged the ultrafast dynamics of Jahn-Teller deformations of CH4+ cation in real space. It is unraveled that the Jahn-Teller deformation from C3v to C2v geometries takes a characteristic time of about 20 femtoseconds for this system. Classical and quantum molecular dynamics simulations agree well with the measurement, and reveal dynamics for the build-up of the C2v structure involving complex phasing process of multiple vibrational pathways of the CH4+ cation.


Author(s):  
Konstantinos Manikas ◽  
Markus Hütter ◽  
Patrick D. Anderson

AbstractThe effect of time-dependent external fields on the structures formed by particles with induced dipoles dispersed in a viscous fluid is investigated by means of Brownian Dynamics simulations. The physical effects accounted for are thermal fluctuations, dipole-dipole and excluded volume interactions. The emerging structures are characterised in terms of particle clusters (orientation, size, anisotropy and percolation) and network structure. The strength of the external field is increased in one direction and then kept constant for a certain amount of time, with the structure formation being influenced by the slope of the field-strength increase. This effect can be partially rationalized by inhomogeneous time re-scaling with respect to the field strength, however, the presence of thermal fluctuations makes the scaling at low field strength inappropriate. After the re-scaling, one can observe that the lower the slope of the field increase, the more network-like and the thicker the structure is. In the second part of the study the field is also rotated instantaneously by a certain angle, and the effect of this transition on the structure is studied. For small rotation angles ($$\theta \le 20^{{\circ }}$$ θ ≤ 20 ∘ ) the clusters rotate but stay largely intact, while for large rotation angles ($$\theta \ge 80^{{\circ }}$$ θ ≥ 80 ∘ ) the structure disintegrates and then reforms, due to the nature of the interactions (parallel dipoles with perpendicular inter-particle vector repel each other). For intermediate angles ($$20<\theta <80^{{\circ }}$$ 20 < θ < 80 ∘ ), it seems that, during rotation, the structure is altered towards a more network-like state, as a result of cluster fusion (larger clusters). The details provided in this paper concern an electric field, however, all results can be projected into the case of a magnetic field and paramagnetic particles.


Author(s):  
Adrian Dominguez-Castro ◽  
Thomas Frauenheim

Theoretical calculations are an effective strategy to comple- ment and understand experimental results in atomistic detail. Ehrenfest molecular dynamics simulations based on the real-time time-dependent density functional tight-binding (RT-TDDFTB) approach...


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