The chemical model of matter consists of atoms held together by bonds. The success of this model implies that the physical interactions of the electrons and nuclei in molecules combine into compound interactions that create the bonding. In the quantum mechanical description, the modified atoms in molecules and the bonding synergism are contained in the molecular electronic wave function. So far, only part of this information has been recovered from the wave function. Notably, the atoms have remained unidentified in the wave function. One reason is that conventional energy decomposition analyses formulate separate model wave functions, independent of the actual wave function, to represent “prepared atoms” and preconceived interactions and, then, intuitively catenate the parts. In the present work, the embedded modified atoms and the inherent physical synergisms between them are determined by a unified derivation entirely from the actual molecular valence space wave function. By means of a series of intrinsic orbital and configurational transformations of the wave function, the energy of formation of a molecule is additively resolved in terms of intra-atomic energy changes, interference energies, and quasi-classical, non-classical, and charge-transfer Coulombic interactions. Here, the analysis furnishes an algorithm for the quantitative resolution of the energy of formation, which enables analyses elucidating reaction energies.
Ruedenberg, Klaus (2022). Atoms and interatomic bonding synergism inherent in molecular electronic wave functions. Journal of Chemical Physics, 157(2). https://doi.org/10.1063/5.0094609
@article{osti_1881915,
author = {Ruedenberg, Klaus},
title = {Atoms and interatomic bonding synergism inherent in molecular electronic wave functions},
annote = {The chemical model of matter consists of atoms held together by bonds. The success of this model implies that the physical interactions of the electrons and nuclei in molecules combine into compound interactions that create the bonding. In the quantum mechanical description, the modified atoms in molecules and the bonding synergism are contained in the molecular electronic wave function. So far, only part of this information has been recovered from the wave function. Notably, the atoms have remained unidentified in the wave function. One reason is that conventional energy decomposition analyses formulate separate model wave functions, independent of the actual wave function, to represent “prepared atoms” and preconceived interactions and, then, intuitively catenate the parts. In the present work, the embedded modified atoms and the inherent physical synergisms between them are determined by a unified derivation entirely from the actual molecular valence space wave function. By means of a series of intrinsic orbital and configurational transformations of the wave function, the energy of formation of a molecule is additively resolved in terms of intra-atomic energy changes, interference energies, and quasi-classical, non-classical, and charge-transfer Coulombic interactions. Here, the analysis furnishes an algorithm for the quantitative resolution of the energy of formation, which enables analyses elucidating reaction energies.},
doi = {10.1063/5.0094609},
url = {https://www.osti.gov/biblio/1881915},
journal = {Journal of Chemical Physics},
issn = {ISSN 0021-9606},
number = {2},
volume = {157},
place = {United States},
publisher = {American Institute of Physics (AIP)},
year = {2022},
month = {07}}
National Science Foundation (NSF); USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
Grant/Contract Number:
AC02-07CH11358
OSTI ID:
1881915
Alternate ID(s):
OSTI ID: 1876148
Report Number(s):
IS-J-10,858; CHE-1565888
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 2 Vol. 157; ISSN 0021-9606
Proceedings of the Royal Society of London. A. Mathematical and Physical Sciences, Vol. 371, Issue 1747, p. 525-552https://doi.org/10.1098/rspa.1980.0095