The conceptual and mathematical foundations of the MC-QTAIM
arXiv:2204.09604 · doi:10.1016/B978-0-12-821978-2.00029-5
Abstract
The concept of atoms in molecules (AIM) is one of the cornerstones of the structural theory of chemistry however, in contrast to the free atoms a comprehensive quantum mechanical theory of AIM has never been proposed. Currently the most satisfactory deduction of this concept is based on the partitioning methodologies that are trying to recover AIM from the ab initio wavefunctions (WF). One of these methodologies is the quantum theory of AIM (QTAIM), which retrieves AIM by an exhaustive partitioning of the one-electron density into atomic basins in real space. The molecular properties are then partitioned into the basin and inter-basin contributions as the incarnation of the AIM properties and their interaction modes. The inputs of the QTAIM partitioning scheme are the electronic WF computed from the electronic Schrodinger equation (SE), which is basically a single-component equation treating electrons as quantum particles and the nuclei as clamped point charges (CPC). A recently extended form of the QTAIM, called the multi-component QTAIM (MC-QTAIM), removes this restriction and enables AIM partitioning to be applied to the MC quantum systems. This is done using MC-WF as inputs that are derived from the MC-SE in which there are two or more types of quantum particles. This opens the possibility for the AIM partitioning of molecular systems where certain nuclei, e.g. because of their non-adiabatic coupling to electrons, must be treated as quantum particles instead of CPC. The same formalism allows the partitioning of exotic molecular systems in which there are other elementary particles like muons or positrons, in addition to electrons and nuclei. The application of the MC-QTAIM partitioning to such systems reveals that the positively charged muon may shape its own atomic basin, i.e. an example of exotic AIM, while positron may act as an agent of bonding, i.e. an example of exotic bonds.
arXiv commentThis is a polished version of v2 draft
References in corpus (24)
- Modern Theory of Nuclear Forces
- Nearsightedness of Electronic Matter
- Quantum Monte Carlo calculations of A=8 nuclei
- Microscopic Clustering in Light Nuclei
- The nucleon-nucleon interaction
- The basic K nuclear cluster K- pp and its enhanced formation in the p + p -> K+ + X reaction
- Toward understanding the microscopic origin of nuclear clustering
- Localization and clustering in the nuclear Fermi liquid
- Multiquark states as di-hadronic molecules
- Nucleon-Nucleon Potentials in Comparison: Physics or Polemics?
- Emergence of simple patterns in many-body systems: from macroscopic objects to the atomic nucleus
- Bound state spectra of three-body muonic molecular ions
- Deciphering the "chemical" nature of the exotic isotopes of Hydrogen by the MC-QTAIM analysis: The positively charged Muon and the Muonic Helium as new members of the Periodic Table
- Hidden aspects of the Structural Theory of chemistry: The MC-QTAIM analysis reveals "alchemical" transformation from a triatomic to a diatomic structure
- Where to place the positive muon in the Periodic Table?
- Revisiting the foundations of the quantum theory of atoms in molecules: Some open problems
- The Two-Component Quantum Theory of Atoms in Molecules (TC-QTAIM): The unified theory of localization/delocalization of electrons, nuclei and exotic elementary particles
- Topological and AIM analyses beyond the Born-Oppenheimer paradigm: New opportunities
- On the nature of the positronic bond
- Colour flux-tubes in static Pentaquark and Tetraquark systems
- Incorporating nuclear vibrational energies into the -atom in molecules- analysis: An analytical study
- Developing effective electronic-only coupled-cluster and Muller-Plesset perturbation theories for the muonic molecules
- The Quest for Pionic and Kaonic Nuclear Bound Systems Following Yukawa and Tomonaga
- Internal clusterization in the Coulomb few-body systems and stability of the five- and six-body systems with unit charges