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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. [ABSTRACT FROM AUTHOR]

A trajectory method of calculating tunneling probabilities from phase integrals along straight line tunneling paths, originally suggested by Makri and Miller [J. Chem. Phys. 91, 4026 (1989)] and recently implemented by Truhlar and co-workers [Chem. Sci. 5, 2091 (2014)], is tested for oneand two-dimensional ab initio based potentials describing hydrogen dissociation in the 1B1 excited electronic state of pyrrole. The primary observables are the tunneling rates in a progression of bending vibrational states lying below the dissociation barrier and their isotope dependences. Several initial ensembles of classical trajectories have been considered, corresponding to the quasiclassical and the quantum mechanical samplings of the initial conditions. It is found that the sampling based on the fixed energy Wigner density gives the best agreement with the quantum mechanical dissociation rates. [ABSTRACT FROM AUTHOR]

We examine the phase space structures that govern reaction dynamics in the absence of critical points on the potential energy surface. We show that in the vicinity of hyperbolic invariant tori, it is possible to define phase space dividing surfaces that are analogous to the dividing surfaces governing transition from reactants to products near a critical point of the potential energy surface. We investigate the problem of capture of an atom by a diatomic molecule and show that a normally hyperbolic invariant manifold exists at large atom-diatom distances, away from any critical points on the potential. This normally hyperbolic invariant manifold is the anchor for the construction of a dividing surface in phase space, which defines the outer or loose transition state governing capture dynamics. We present an algorithm for sampling an approximate capture dividing surface, and apply our methods to the recombination of the ozone molecule. We treat both 2 and 3 degrees of freedom models with zero total angular momentum. We have located the normally hyperbolic invariant manifold from which the orbiting (outer) transition state is constructed. This forms the basis for our analysis of trajectories for ozone in general, but with particular emphasis on the roaming trajectories. [ABSTRACT FROM AUTHOR]

Despite using potential energy surfaces, multivariable functions on molecular configuration space, to comprehend chemical dynamics for decades, the real happenings in molecules occur in phase space, in which the states of a classical dynamical system are completely determined by the coordinates and their conjugate momenta. Theoretical and numerical results are presented, employing alanine dipeptide as a model system, to support the view that geometrical structures in phase space dictate the dynamics of molecules, the fingerprints of which are traced by following the Hamiltonian flow above saddles. By properly selecting initial conditions in alanine dipeptide, we have found internally free rotor trajectories the existence of which can only be justified in a phase space perspective.This article is part of the theme issue 'Modern theoretical chemistry'., (© 2018 The Author(s).)