Role of Topological Phases in Quantum Molecular Dynamics
Assoc. Professor, Department of Chemistry
University of Toronto
Friday, March 8, 2019
C2-361 (Reading Room)
Dynamical consideration that goes beyond the common Born−Oppenheimer approximation (BOA) becomes necessary when energy differences between electronic potential energy surfaces become small or vanish. One of the typical scenarios of the BOA breakdown in molecules beyond diatomics is a conical intersection (CI) of electronic potential energy surfaces. CIs provide an efficient mechanism for radiationless electronic transitions: acting as “funnels” for the nuclear wave function, they enable rapid conversion of the excessive electronic energy into the nuclear motion. In addition, CIs introduce nontrivial topological or Berry phases for both electronic and nuclear wave functions. These phases manifest themselves in change of the wave function signs if one considers an evolution of the system around the CI. This sign change is independent of the shape of the encircling contour and thus has a topological character. How these extra phases affect nonadiabatic dynamics is the main question that is addressed in this lecture.
I start by considering the simplest model providing the CI topology: two-dimensional two-state linear vibronic coupling model. Selecting this model instead of a real molecule has the advantage that various dynamical regimes can be easily modeled in the model by varying parameters, whereas any fixed molecule provides the system specific behavior that may not be very illustrative. After demonstrating when topological phase effects are important and how they modify the dynamics for two sets of initial conditions (starting from the ground and excited electronic states), we give examples of molecular systems where the described topological phase effects are crucial for adequate description of nonadiabatic dynamics.
Understanding an extent of changes introduced by the topological phase in chemical dynamics poses a problem of capturing its effects by approximate methods of simulating nonadiabatic dynamics that can go beyond simple models. I assess the performance of both fully quantum (wave packet dynamics) and quantum-classical (surface-hopping, Ehrenfest, and quantum-classical Liouville equation) approaches in various cases where topological phase effects are important. It has been identified that the key to success in approximate methods is a method organization that prevents the quantum nuclear kinetic energy operator to act directly on adiabatic electronic wave functions.
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