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We investigate from a theoretical point of view the stability of AlN2+ and GaN2+ 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 11Δ 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 AlN2+ and GaN2+ is completely different despite the strong resemblance of their electronic structure. [ABSTRACT FROM AUTHOR]

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 AlN2+ and GaN2+ dications emitted from an Al0.25Ga0.75N sample in a joint theoretical and experimental study. Despite the strong chemical resemblance of these two molecules, we observe only stable AlN2+, while GaN2+ 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 GaN2+, the relatively small electric dipole of the dication in its ground 13Σ− and excited 11Δ 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 AlN2+ mechanical dissociation leads to Al2+ + 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. [ABSTRACT FROM AUTHOR]

The molecular electronic states of the SiO2+ 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 Si2+ + O dissociation channels. These patterns are recorded and observed experimentally in a correlated time-of-flight map. [ABSTRACT FROM AUTHOR]

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.