Conical Intersections and Avoided Crossings of Electronic Energy Levels

We study the unique phenomena which occur in certain systems characterized by the crossing or avoided crossing of two electronic eigenvalues. First, an example problem will be investigated for a given Hamiltonian resulting in a codimension 1 crossing by implementing results by Hagedorn from 1994. Then we perturb the Hamiltonian to study the system for the corresponding avoided crossing by implementing results by Hagedorn and Joye from 1998. The results from these demonstrate the behavior which occurs at a codimension 1 crossing and avoided crossing and illustrates the differences. These solutions may also be used in further studies with Herman-Kluk propagation and more. Secondly, we study codimension 2 crossings by considering a more general type of wave packet. We focus on the case of Schrödinger equation but our methods are general enough to be adapted to other systems with the geometric conditions therein. The motivation comes from the construction of surface hopping algorithms giving an approximation of the solution of a system of Schrödinger equations coupled by a potential admitting a conical intersection, in the spirit of Herman-Kluk approximation (in close relation with frozen/thawed approximations). Our main Theorem gives explicit transition formulas for the profiles when passing through a conical crossing point, including precise computation of the transformation of the phase and its proof is based on a normal form approach.

Name thesis:degree_name

Doctor of Philosophy

Level thesis:degree_level

doctoral

Discipline thesis:degree_discipline

Mathematics

Department dc:contributor.department

Mathematics

Grantor dc:publisher

Virginia Tech

Year dc:date.issued

2021

Author dc:creator

• Gamble, Stephanie Nicole

Chair dc:contributor.committeechair

• Hagedorn, George A.

Committee members dc:contributor.committeemember

• Fermanian Kammerer, Clotilde
• Elgart, Alexander
• Klaus, Martin
• Valeyev, Eduard Faritovich

• quantum mechanics
• conical intersections
• energy level crossings
• avoided crossings
• semiclassical wave packets
• propagation of coherent states

Statement dc:rights

• In Copyright

Licence dc:rights.uri

• http://rightsstatements.org/vocab/InC/1.0/

Dc Identifier Other

vt_gsexam:29059

OAI identifier oai:identifier

oai:vtechworks.lib.vt.edu:10919/101899