First-principle molecular dynamics of the Berry pseudorotation: insights on 19F NMR in SF4.
First-principles [density-functional theory (DFT)] molecular-dynamic simulations of the Berry pseudorotation mechanism in SF4 were performed using the atom-centered density-matrix propagation method. The reaction was monitored by following the chemical shieldings of the fluorine atoms, computed on snapshots along the trajectories. In particular we compared the results obtained using a standard functional based on the generalized gradient approximation with those issuing from its hybrid Hartree-Fock-DFT counterpart using a number of basis sets. Our results show that both the basis set and the functional choice rule the quality of the molecular properties monitored as well as the trajectory over the potential-energy surface.
Laboratorio di Struttura e Dinamica Molecolare, Dipartimento di Chimica, Complesso Universitario Monte Sant'Angelo, Via Cintia, I-80126 Naples, Italy.
Michele
M
Pavone
Vincenzo
V
Barone
Ilaria
I
Ciofini
Carlo
C
Adamo