title: Modeling the influence of a laser pulse on the potential energy surface in optimal molecular control theory.
abstract: Understanding and modeling the interaction between light and matter is essential to the theory of optical molecular control. While the effect of the electric field on a molecule's electronic structure is often not included in control theory, it can be modeled in an optimal control algorithm by a set or toolkit of potential energy surfaces indexed by discrete values of the electric field strength where the surfaces are generated by Born-Oppenheimer electronic structure calculations that directly include the electric field. Using a new optimal control algorithm with a trigonometric mapping to limit the maximum field strength explicitly, we apply the surface-toolkit method to control the hydrogen fluoride molecule. Potential energy surfaces in the presence and absence of the electric field are created with two-electron reduced-density-matrix techniques. The population dynamics show that adjusting for changes in the electronic structure of the molecule beyond the static dipole approximation can be significant for designing a field that drives a realistic quantum system to its target observable.
authors.affiliation: Department of Chemistry, The University of Chicago, Chicago, IL 60637, USA.
authors.forename: John D
authors.initials: JD
authors.lastname: Farnum
authors.forename: Gergely
authors.initials: G
authors.lastname: Gidofalvi
authors.forename: David A
authors.initials: DA
authors.lastname: Mazziotti