Nonadiabatic nuclear dynamics of the ammonia cation studied by surface hopping classical trajectory calculations.

@article{Belyaev2014NonadiabaticND,
  title={Nonadiabatic nuclear dynamics of the ammonia cation studied by surface hopping classical trajectory calculations.},
  author={Andrey K. Belyaev and Wolfgang Domcke and Caroline Lasser and Giulio Trigila},
  journal={The Journal of chemical physics},
  year={2014},
  volume={142 10},
  pages={
          104307
        }
}
The Landau-Zener (LZ) type classical-trajectory surface-hopping algorithm is applied to the nonadiabatic nuclear dynamics of the ammonia cation after photoionization of the ground-state neutral molecule to the excited states of the cation. The algorithm employs a recently proposed formula for nonadiabatic LZ transition probabilities derived from the adiabatic potential energy surfaces. The evolution of the populations of the ground state and the two lowest excited adiabatic states is calculated… 
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References

SHOWING 1-10 OF 45 REFERENCES

Photoionization-induced dynamics of the ammonia cation studied by wave packet calculations using curvilinear coordinates

Photoionization-induced dynamics of ammonia: ab initio potential energy surfaces and time-dependent wave packet calculations for the ammonia cation.

An analytical anharmonic six-dimensional three-sheeted potential energy surface for the ground and first excited states of the ammonia cation has been developed which is tailored to model the…

Landau-Zener type surface hopping algorithms.

A class of surface hopping algorithms is studied comparing two recent Landau-Zener (LZ) formulas for the probability of nonadiabatic transitions, which confirm the affinity of both the LZ probabilities, as well as the good approximation of the reference solution computed by solving the Schrödinger equation via a grid based pseudo-spectral method.

Surface-hopping modeling of photoinduced relaxation dynamics on coupled potential-energy surfaces

A mixed quantum-classical description of nonadiabatic photoreactions such as internal conversion and electron transfer is outlined. In particular the validity and limitations of Tully’s…

Trajectory Surface Hopping Approach to Nonadiabatic Molecular Collisions: The Reaction of H+ with D2

An extension of the classical trajectory approach is proposed that may be useful in treating many types of nonadiabatic molecular collisions. Nuclei are assumed to move classically on a single…

Trajectory Surface Hopping Study of the Li + Li2(X1Σg+) Dissociation Reaction

Trajectory surface hopping calculations are reported for the Li + Li2(X1Σg+) dissociation reaction over the range of translational energies 13 ≤ Etr/kcal mol-1 ≤ 80. Both potential energy surfaces…

Molecular dynamics with electronic transitions

A method is proposed for carrying out molecular dynamics simulations of processes that involve electronic transitions. The time dependent electronic Schrodinger equation is solved self‐consistently…

Semiclassical Theory of Electronic Transitions in Low Energy Atomic and Molecular Collisions Involving Several Nuclear Degrees of Freedom

A semiclassical theory is developed for describing electronic transitions in low energy atomic and molecular collisions, such as A+BC, that involve quantized nuclear degrees of freedom (i.e.,…

Dynamics of metal electron excitation in atom-surface collisions: A quantum wave packet approach

Approximate switching algorithms for trajectory surface hopping.