Frozen Gaussian approximation with surface hopping for mixed quantum-classical dynamics: A mathematical justification of fewest switches surface hopping algorithms
This work provides a theoretical foundation for widely used surface hopping methods in computational chemistry, addressing a long-standing gap in mathematical understanding.
The authors developed a surface hopping algorithm for mixed quantum-classical dynamics, providing rigorous error analysis and showing it is a path integral stochastic representation of semiclassical matrix Schrödinger equations, thereby offering mathematical justification for Tully's fewest switches surface hopping methods.
We develop a surface hopping algorithm based on frozen Gaussian approximation for semiclassical matrix Schrödinger equations, in the spirit of Tully's fewest switches surface hopping method. The algorithm is asymptotically derived from the Schrödinger equation with rigorous approximation error analysis. The resulting algorithm can be viewed as a path integral stochastic representation of the semiclassical matrix Schrödinger equations. Our results provide mathematical understanding to and shed new light on the important class of surface hopping methods in theoretical and computational chemistry.