Hamiltonian Computational Chemistry: Geometrical Structures in Chemical Dynamics and Kinetics

Abstract

The common geometrical (symplectic) structures of classical mechanics, quantum mechanics, and classical thermodynamics are unveiled with three pictures. These cardinal theories, mainly at the non-relativistic approximation, are the cornerstones for studying chemical dynamics and chemical kinetics. Working in extended phase spaces, we show that the physical states of integrable dynamical systems are depicted by Lagrangian submanifolds embedded in phase space. Observable quantities are calculated by properly transforming the extended phase space onto a reduced space, and trajectories are integrated by solving Hamilton’s equations of motion. After defining a Riemannian metric, we can also estimate the length between two states. Local constants of motion are investigated by integrating Jacobi fields and solving the variational linear equations. Diagonalizing the symplectic fundamental matrix, eigenvalues equal to one reveal the number of constants of motion. For conservative systems, geometrical quantum mechanics has proved that solving the Schrödinger equation in extended Hilbert space, which incorporates the quantum phase, is equivalent to solving Hamilton’s equations in the projective Hilbert space. In classical thermodynamics, we take entropy and energy as canonical variables to construct the extended phase space and to represent the Lagrangian submanifold. Hamilton’s and variational equations are written and solved in the same fashion as in classical mechanics. Solvers based on high-order finite differences for numerically solving Hamilton’s, variational, and Schrödinger equations are described. Employing the Hénon–Heiles two-dimensional nonlinear model, representative results for time-dependent, quantum, and dissipative macroscopic systems are shown to illustrate concepts and methods. High-order finite-difference algorithms, despite their accuracy in low-dimensional systems, require substantial computer resources when they are applied to systems with many degrees of freedom, such as polyatomic molecules. We discuss recent research progress in employing Hamiltonian neural networks for solving Hamilton’s equations. It turns out that Hamiltonian geometry, shared with all physical theories, yields the necessary and sufficient conditions for the mutual assistance of humans and machines in deep-learning processes.