Direct calculation of coupled diabatic potential-energy surfaces for ammonia and mapping of a four-dimensional conical intersection seam

Shikha Nangia, Donald G. Truhlar

Research output: Contribution to journalArticle

55 Scopus citations

Abstract

We used multiconfiguration quasidegenerate perturbation theory and the fourfold-way direct diabatization scheme to calculate ab initio potential-energy surfaces at 3600 nuclear geometries of NH3. The calculations yield the adiabatic and diabatic potential-energy surfaces for the ground and first electronically excited singlet states and also the diabatic coupling surfaces. The diabatic surfaces and coupling were fitted analytically to functional forms to obtain a permutationally invariant 2×2 diabatic potential-energy matrix. An analytic representation of the adiabatic potential-energy surfaces is then obtained by diagonalizing the diabatic potential-energy matrix. The analytic representation of the surfaces gives an analytic representation of the four-dimensional conical intersection seam which is discussed in detail.

Original languageEnglish (US)
Article number124309
JournalThe Journal of Chemical Physics
Volume124
Issue number12
DOIs
StatePublished - 2006
Externally publishedYes

    Fingerprint

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this