The parallel-transported (quasi)-diabatic basis

• Published in: The Journal of chemical physics 2022-11, Vol.157 (18), p.184303-184303
• Main Authors: Littlejohn, Robert, Rawlinson, Jonathan, Subotnik, Joseph
• Format: Article
• Language: English
• Subjects: Couplings; Curvature; Electromagnetism; Fine structure; Operators (mathematics); Power series; Schrodinger equation; Series expansion; Taylor series
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/5.0122781

This article concerns the use of parallel transport to create a diabatic basis. The advantages of the parallel-transported basis include the facility with which Taylor series expansions can be carried out in the neighborhood of a point or a manifold such as a seam (the locus of degeneracies of the electronic Hamiltonian), and the close relationship between the derivative couplings and the curvature in this basis. These are important for analytic treatments of the nuclear Schrödinger equation in the neighborhood of degeneracies. The parallel-transported basis bears a close relationship to the singular-value basis; in this article, both are expanded in power series about a reference point and are shown to agree through second order but not beyond. Taylor series expansions are effected through the projection operator, whose expansion does not involve energy denominators or any type of singularity and in terms of which both the singular-value basis and the parallel-transported basis can be expressed. The parallel-transported basis is a version of Poincaré gauge, well known in electromagnetism, which provides a relationship between the derivative couplings and the curvature and which, along with a formula due to Mead, affords an efficient method for calculating Taylor series of the basis states and the derivative couplings. The case in which fine structure effects are included in the electronic Hamiltonian is covered.