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A QTAIM and stress tensor perspective of large‐amplitude motions of the tetrasulfur tetranitride S 4 N 4 molecular graph
Author(s) -
Xu Yuning,
Xu Tianlv,
Jiajun Dong,
Kirk Steven R.,
Jenkins Samantha
Publication year - 2016
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.25122
Subject(s) - cauchy stress tensor , tensor (intrinsic definition) , polarizability , topology (electrical circuits) , chemistry , physics , quantum mechanics , mathematics , geometry , molecule , combinatorics
The nature of the bonding interactions including the intramolecular SS interactions in tetrasulfur tetranitride, S 4 N 4 are probed by performing very large amplitude vibrations of all of the 18 normal modes of vibration. The QTAIM and stress tensor point properties are ‐then investigated and found to be highly dependent on the mode of vibration. A considerable degree of metallicity ξ( r b ) is found for the SS and SN bonding interactions. A unique bonding feature is found for a small amplitude vibration of the most anharmonic mode of this investigation, mode 2, where the SS bond critical point (BCP) transforms from a closed‐shell SS BCP to a shared‐shell SS BCP. We find 17 new unique QTAIM topologies for the molecular graphs corresponding to the 18 modes of vibration along with seven “missing” topologies that are mapped onto a spanning 2‐D Quantum topology Phase Diagram (QTPD). In addition, eleven unique topologies existing on 3‐D QTPDs are found due to the presence of non‐nuclear attractors (NNAs). We use the stress tensor eigenvalues to explain the invariance of the numbers and types of QTAIM critical points. The applicability of both the stiffness S and stress tensor stiffness S σ are also explored. Two new bond measures are introduced, a polarizability P and the stress tensor polarizability P σ which are derived from the stiffness S and stress tensor stiffness S σ , respectively. © 2016 Wiley Periodicals, Inc.