On the Quantum Theory of Molecules

Abstract

Transition state theory was introduced in the 1930s to account for chemical reactions. Central to this theory is the idea of a potential energy surface (PES). It was assumed that such a surface could be constructed using eigensolutions of the Schrödinger equation for the molecular (Coulomb) Hamiltonian but at that time such calculations were not possible. Nowadays quantum mechanical ab-initio electronic structure calculations are routine and from their results PESs can be constructed which are believed to approximate those assumed derivable from the eigensolutions. It is argued here that this belief is unfounded. It is suggested that the potential energy surface construction is more appropriately regarded as a legitimate and effective modification of quantum mechanics for chemical purposes

Cited by in corpus (18)

• Pre-Born-Oppenheimer Molecular Structure Theory
• Heisenberg's uncertainty principle in the PTOLEMY project: a theory update
• Singularity avoidance in a quantum model of the Mixmaster universe
• Smooth Quantum Dynamics of Mixmaster Universe
• On the mathematical treatment of the Born-Oppenheimer approximation
• Vibronic framework for quantum mixmaster universe
• Comment on `On the Quantum Theory of Molecules' [J. Chem.Phys. {\bf 137}, 22A544 (2012)]
• Density Functional Theory of Material Design: Fundamentals and Applications -- I
• On Factorization of Molecular Wavefunctions
• Strong Coupling Thermodynamics and Stochastic Thermodynamics from the Unifying Perspective of Time-Scale Separation
• Laser-induced dynamic alignment of the HD molecule without the Born-Oppenheimer approximation
• Potential energy surfaces in atomic structure: The role of Coulomb correlation in the ground state of helium
• Understanding polaritonic chemistry from ab initio quantum electrodynamics
• On the impossibility of frozen nuclei
• Characterization of the continuous transition from atomic to molecular shape in the three-body Coulomb system
• Quantum-ionic features in the absorption spectra of homonuclear diatomic molecules
• On the four-body problem in the Born-Oppenheimer approximation
• Perspective on Moreau-Yosida Regularization in Density-Functional Theory