Non-adiabatic effects in the H₃⁺ spectrum.

ABSTRACT: The effect of non-adiabatic coupling on the computed rovibrational energy levels amounts to about 2 cm^-1 for H₃⁺ and must be included in high-accuracy calculations. Different strategies to obtain the corresponding energy shifts are reviewed in the article. A promising way is to introduce effective vibrational reduced masses that depend on the nuclear configuration. A new empirical method that uses the stockholder atoms-in-molecules approach to this effect is presented and applied to H₃⁺. Furthermore, a highly accurate potential energy surface for the D₃⁺ isotopologue, which includes relativistic and leading quantum electrodynamic terms, is constructed and used to analyse the observed rovibrational frequencies for

SUBMITTER: Amaral PHR 

PROVIDER: S-EPMC6710893 | biostudies-literature | 2019 Sep

REPOSITORIES: biostudies-literature