Premium
Electron nuclear dynamics studies of H 3 and H 3 +
Author(s) -
Hagelberg F.
Publication year - 1999
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/(sici)1097-461x(1999)75:4/5<367::aid-qua4>3.0.co;2-3
Subject(s) - pseudorotation , chemistry , wave function , excited state , atomic physics , electronic structure , electron , degeneracy (biology) , quantum mechanics , physics , computational chemistry , molecule , bioinformatics , biology
The electron nuclear dynamics (END) theory is used to study various processes involving the disintegration of a H 3 and the pseudorotation of the H 3 +ion. The former system is prepared in an initial state of equilateral geometry which is associated with a degeneracy of the electronic system. The electronic wave function is initially defined as a representation of either of the D 3 h doublet components; the corresponding dynamical features are considered in terms of nuclear trajectories for both cases. Disintegration out of a rotating state is shown to yield periodic electronic spin exchange between two bonding H atoms, which is interpreted as a signature of nonadiabatic behavior. Possible applications of this phenomenon in the study of molecular dissociation is discussed. The bound system H 3 +is explored under the aspect of pseudorotational motion. Different dynamic regimes are explored; it is shown that the limiting case of circular pseudorotation can be approximated through the choice of an initial nuclear distortion momentum of magnitude P ≈1.7 au. For sizably smaller momenta, the motion is dominated by one distortion mode only; for larger momenta, pseudoprecession results. These dynamic phenomena find their electronic counterparts in cyclical charge waves excited in the electronic system. ©1999 John Wiley & Sons, Inc. Int J Quant Chem 75: 367–383, 1999