TY - JOUR

T1 - Topology vs. thermodynamics in chemical reactions

T2 - the instability of PH5

AU - Tantardini, Christian

AU - Benassi, Enrico

N1 - Publisher Copyright: © the Owner Societies 2017.

PY - 2017/9/25

Y1 - 2017/9/25

N2 - The topological approach, based on Bader theory, is compared to the common thermodynamical methodology to study chemical reactivity. It is shown how the former indeed has numerous advantages and provides a more detailed description with respect to the latter about the course of the reaction. The comparison between the two approaches is performed by considering a classical reaction, i.e. the decomposition of PX5 (X = H, F). The topological investigation was supported by using different state-of-the-art topological tools, such as the source function, Espinosa indexes, delocalisation indexes, and domain-averaged Fermi hole analysis. Furthermore, in this work a new topological descriptor, the Bader energy density, PBADER, is introduced and applied to the study case. For the first time since Bader theory was introduced, the distribution of atomic energies in the atomic basins was analysed in detail and used to explain the chemical reactivity a priori.

AB - The topological approach, based on Bader theory, is compared to the common thermodynamical methodology to study chemical reactivity. It is shown how the former indeed has numerous advantages and provides a more detailed description with respect to the latter about the course of the reaction. The comparison between the two approaches is performed by considering a classical reaction, i.e. the decomposition of PX5 (X = H, F). The topological investigation was supported by using different state-of-the-art topological tools, such as the source function, Espinosa indexes, delocalisation indexes, and domain-averaged Fermi hole analysis. Furthermore, in this work a new topological descriptor, the Bader energy density, PBADER, is introduced and applied to the study case. For the first time since Bader theory was introduced, the distribution of atomic energies in the atomic basins was analysed in detail and used to explain the chemical reactivity a priori.

KW - AVERAGED FERMI HOLES

KW - HYPERVALENT MOLECULES

KW - ELECTRON-DENSITY

KW - WAVE-FUNCTIONS

KW - BOND

KW - CRYSTALS

KW - CLUSTERS

KW - ENERGY

KW - MODEL

KW - WEAK

UR - http://www.scopus.com/inward/record.url?scp=85049151101&partnerID=8YFLogxK

U2 - 10.1039/c7cp06130g

DO - 10.1039/c7cp06130g

M3 - Article

C2 - 28990031

AN - SCOPUS:85049151101

VL - 19

SP - 27779

EP - 27785

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

SN - 1463-9076

IS - 40

ER -