The MC-QTAIM analysis reveals an exotic bond in the coherently quantum superposed Malonaldehyde
arXiv:2205.12090 · doi:10.1039/D2CP05499J
Abstract
The proton between the two oxygen atoms of the malonaldehyde molecule experiences an effective double-well potential in which the proton wavefunction is delocalized between the two wells. Herein we employed the state-of-the-art multi-component quantum theory of atoms in molecules partitioning scheme to obtain the molecular structure, i.e. atoms in molecules and bonding network, from the superposed ab initio wavefunctions of malonaldehyde. In contrast to the familiar clamped-proton portrayal of malonaldehyde, in which the proton forms a hydrogen basin, for the superposed states the hydrogen basin disappears and two novel hybrid oxygen-hydrogen basins appear instead, with an even distribution of the proton population between the two basins. The interaction between the hybrid basins is stabilizing thanks to an unprecedented mechanism. This involves the stabilizing classical Coulomb interaction of the one-proton density in one of the basins with the one-electron density in the other basin. This stabilizing mechanism yields a bond foreign to the known bonding modes in chemistry.
arXiv commentFile contains the main text plus the supporting information
References in corpus (15)
- Development of a Practical Multicomponent Density Functional for Electron-Proton Correlation to Produce Accurate Proton Densities
- Hund's paradox and the collisional stabilization of chiral molecules
- Interaction induced localization in a gas of pyramidal molecules
- 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?
- 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
- Two-component density functional theory for muonic molecules: Inclusion of the electron-positive muon correlation functional
- Spontaneous symmetry breaking: variations on a theme
- 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
- Spontaneous symmetry breaking and inversion-line spectroscopy in gas mixtures
- Quantum molecular dynamics study of the pressure dependence of the ammonia inversion transition