Transition states, reaction paths, and thermochemistry using the nuclear–electronic orbital analytic Hessian

Abstract

The nuclear–electronic orbital (NEO) method is a multicomponent quantum chemistry theory that describes electronic and nuclear quantum effects simultaneously while avoiding the Born–Oppenheimer approximation for certain nuclei. Typically specified hydrogen nuclei are treated quantum mechanically at the same level as the electrons, and the NEO potential energy surface depends on the classical nuclear coordinates. This approach includes nuclear quantum effects such as zero-point energy and nuclear delocalization directly into the potential energy surface. An extended NEO potential energy surface depending on the expectation values of the quantum nuclei incorporates coupling between the quantum and classical nuclei. Herein, theoretical methodology is developed to optimize and characterize stationary points on the standard or extended NEO potential energy surface, to generate the NEO minimum energy path from a transition state down to the corresponding reactant and product, and to compute thermochemical properties. For this purpose, the analytic coordinate Hessian is developed and implemented at the NEO Hartree–Fock level of theory. These NEO Hessians are used to study the S_N2 reaction of ClCH₃Cl⁻ and the hydride transfer of C₄H₉⁺. For each system, analysis of the single imaginary mode at the transition state and the intrinsic reaction coordinate along the minimum energy path identifies the dominant nuclear motions driving the chemical reaction. Visualization of the electronic and protonic orbitals along the minimum energy path illustrates the coupled electronic and protonic motions beyond the Born–Oppenheimer approximation. This work provides the foundation for applying the NEO approach at various correlated levels of theory to a wide range of chemical reactions.