3-D bond-paths of QTAIM and the stress tensor in neutral lithium clusters, Lim (m = 2–5), presented on the Ehrenfest force molecular graph

Abstract

In this investigation we set out to understand the origins of non-nuclear attractors (NNAs) found for neutral lithium clusters Li_m (m = 2–5) on the QTAIM molecular graph but not on the Ehrenfest force F(r) molecular graph. Therefore, we pursued the stress tensor σ(r) without using the dependency on the QTAIM partitioning, since previously σ(r) was only calculated within the QTAIM partitioning, to see if any indication of NNA character can be determined. Because the stress tensor σ(r) lacks an associated scalar- or vector-field as is the case for QTAIM and the Ehrenfest F(r) partitioning schemes respectively, a stress tensor σ(r) partitioning scheme cannot be constructed. Therefore, to overcome this difficulty we use next generation QTAIM, constructed from the most preferred directions of electronic charge density accumulation, to calculate the stress tensor σ(r) 3-D bond-paths on the Ehrenfest force F(r) molecular graph. Using next generation 3-D bond-paths within the Ehrenfest force F(r) partitioning, we can classify the degree of NNA character in the absence of NNAs. A much higher degree of NNA character is found to be present for the stress tensor σ(r) 3-D bond-paths than for the corresponding QTAIM or Ehrenfest force F(r) 3-D bond-paths. The stabilizing effect of the NNA is demonstrated by undertaking Li₂ bond-path compression and stretching distortions sufficient to cause the annihilation of the NNA. The compression and stretching distortions also lead to a large increase in the 3-D bond-path asymmetry and persistent bond-path torsion respectively.