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We present a modification to self-consistent charge density functional-based tight binding (SCC-DFTB), which allows computation based on approximate atomic charges. We obtain these charges by means of a machine learning (ML) process that combines a Coulomb model with a neural network. This allows us to avoid the SCC cycles in the SCC-DFTB calculation while maintaining its accuracy. The main input of the model is the atomic positions characterized by a set of atom-centered symmetry functions. The charge inference from our ML algorithm is as close as 10 -2 units of charge from the exact SCC solution. Our ML-DFTB approach provides a good approximation of the density matrix and of the energy and forces with only a single diagonalization. This is a significant computational saving with respect to the complete SCC algorithm, which allows us to investigate a bigger ensemble of atoms. We show the quality of our approach in the case of charged silicon carbide (SiC) clusters. The ML-DFTB potential energy surface (PES) mimics the SCC-DFTB PES rather well, despite its simplicity. This allows us to obtain the same geometric structure ordering with respect to energy for small clusters. The dissociation barriers for ion emission are well-reproduced, which opens the way to investigating ion field emission and charged cluster stability. The ML-DFTB approach is obviously not limited to charged clusters or SiC materials. It opens a new route to investigate larger clusters than those investigated by standard SCC-DFTB, as well as surface and solid-state chemistry at the atomic level.

The use of a tip-shaped sample for the atom probe tomography technique offers the unique opportunity to analyze the dynamics of molecular ions in strong DC fields. We investigate here the stability of AlN 2+ and GaN 2+ dications emitted from an Al 0.25 Ga 0.75 N sample in a joint theoretical and experimental study. Despite the strong chemical resemblance of these two molecules, we observe only stable AlN 2+ , while GaN 2+ can only be observed as a transient species. We simulate the emission dynamics of these ions on field-perturbed potential energy surfaces obtained from quantum chemical calculations. We show that the dissociation is governed by two independent processes. For all bound states, a mechanical dissociation is induced by the distortion of the potential energy surface in the close vicinity of the emitting tip. In the specific case of GaN 2+ , the relatively small electric dipole of the dication in its ground 1 3 Σ - and excited 1 1 Δ states induces a weak coupling with the electric field so that the mechanical dissociation into Ga + + N + lasts for sufficient time to be observed. By contrast, the AlN 2+ mechanical dissociation leads to Al 2+ + N which cannot be observed as a correlated event. For some deeply bound singlet excited states, the spin-orbit coupling with lower energy triplet states gives another chance of dissociation by system inter-system crossing with specific patterns observed experimentally in a correlated time of flight map.

We investigate from a theoretical point of view the stability of AlN 2+ and GaN 2+ dications produced under high static electric fields like those reached in Atom Probe Tomography (APT) experiments. By means of quantum chemical calculations of the electronic structure of these molecules, we show that their stability is governed by two independent processes. On the one hand, the spin-orbit coupling allows some molecular excited states to dissociate by inter-system crossing. On the other hand, the action of the electric field lowers the potential energy barrier, which ensures the dication stability in standard conditions. We present a detailed example of field emission dynamics in the specific case of the 1 1 Δ states for a parabolic tip, which captures the essentials of the process by means of a simplified model. We show that the dissociation dynamics of AlN 2+ and GaN 2+ is completely different despite the strong resemblance of their electronic structure.

The molecular electronic states of the SiO 2+ dication have been investigated in a joint theoretical and experimental analysis. The use of a tip-shaped sample for tomographic atom probe analysis offers the unique opportunity to produce and to analyze the lifetime of some excited states of this dication. The perturbation brought by the large electric field of the polarized tip along the ion trajectory is analyzed by means of molecular dynamics simulation. For the typical electric fields used in the experiment, the lowest energy triplet states spontaneously dissociate, while the lowest energy singlet states do not. We show that the emission process leads to the formation of some excited singlet state, which dissociates by means of spin-orbit coupling with lower-energy triplet states to produce specific patterns associated with Si + + O + and Si 2+ + O dissociation channels. These patterns are recorded and observed experimentally in a correlated time-of-flight map.

The effect of intense ultrashort irradiation on interatomic forces, crystal stability, and possible melting transition of the underlying lattice is not completely elucidated. By using ab initio linear response to compute the phonon spectrum of gold, silicon, and aluminum, we found that silicon and gold behave in opposite ways when increasing radiation intensity: whereas a weakening of the silicon bond induces a lattice instability, gold undergoes a sharp increase of its melting temperature, while a significantly smaller effect is observed for aluminum for electronic temperatures up to 6 eV.

Using a combination of classical and ab-initio molecular dynamics simulations, we calculate the structure and the electrical conductivity of warm dense gold during the first picoseconds after a short-pulse laser illumination. We find that the ions remain in their initial fcc structure for several picoseconds, despite electron temperatures ranging from a few to several eV after the laser illumination. The electrical conductivities calculated under these nonequilibrium conditions and using the latter assumption are in remarkable agreement with recent measurements using a short-pulse laser interacting with gold thin films.