Explicitly correlated potential energy surface of H3+, including relativistic and adiabatic corrections.
After a short historical account of the theory of the H3+ ion, two ab initio methods are reviewed that allow the computation of the ground-state potential energy surface (PES) of H3+ in the Born-Oppenheimer (BO) approximation, with microhartree or even sub-microhartree accuracy, namely the R12 method and the method of explicitly correlated Gaussians. The BO-PES is improved by the inclusion of relativistic effects and adiabatic corrections. It is discussed how non-adiabatic effects on rotation and vibration can be simulated by corrections to the moving nuclear masses. The importance of the appropriate analytic fit to the computed points of the PES for the subsequent computation of the rovibronic spectrum is addressed. Some recent extensions of the computed PES in the energy region above the barrier to linearity are reviewed. This involves a large set of input geometries and the correct treatment of the dissociation asymptotics, including the coupling with the first excited singlet state. Some comments on this state as well as on the lowest triplet state of H3+ are made. The paper ends with a few remarks on the ion H5+.
Kutzelnigg
Werner
W
Lehrstuhl für Theoretische Chemie, Ruhr-Universität Bochum, 44780 Bochum, Germany. werner.kutzelnigg@ruhr-uni-bochum.de
Jaquet
Ralph
R