Energy components in energy decomposition analysis (EDA) are path functions; why does it matter?

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216224%3A14310%2F20%3A00117262" target="_blank" >RIV/00216224:14310/20:00117262 - isvavai.cz</a>

Výsledek na webu

<a href="https://doi.org/10.1039/D0CP04016A" target="_blank" >https://doi.org/10.1039/D0CP04016A</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/d0cp04016a" target="_blank" >10.1039/d0cp04016a</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Energy components in energy decomposition analysis (EDA) are path functions; why does it matter?

Popis výsledku v původním jazyce

Here, we discuss that unlike bond dissociation energy (BDE) that is a state function quantity, the energy components of the energy decomposition analysis (EDA), i.e. electrostatic interaction, Pauli repulsion, and orbital interaction, are path (process) function quantities. Being a path function means that EDA energy components are not uniquely defined, i.e. the relative magnitudes of the orbital interaction, Pauli repulsion, and electrostatic components may vary depending on the selected pathway for EDA. Therefore, at best, EDA can define whether closely related chemical bonds are more or less ionic/covalent compared with each other. However, a precise assessment of the nature of a certain type of chemical bond using EDA is a questionable task. Besides, we briefly discuss that the widely used EDA pathway, which is merely an arbitrary choice among infinite possible paths, comes to conclusions not consistent with our widely accepted knowledge of bond formation even for the simplest molecules.

Název v anglickém jazyce

Energy components in energy decomposition analysis (EDA) are path functions; why does it matter?

Popis výsledku anglicky

Here, we discuss that unlike bond dissociation energy (BDE) that is a state function quantity, the energy components of the energy decomposition analysis (EDA), i.e. electrostatic interaction, Pauli repulsion, and orbital interaction, are path (process) function quantities. Being a path function means that EDA energy components are not uniquely defined, i.e. the relative magnitudes of the orbital interaction, Pauli repulsion, and electrostatic components may vary depending on the selected pathway for EDA. Therefore, at best, EDA can define whether closely related chemical bonds are more or less ionic/covalent compared with each other. However, a precise assessment of the nature of a certain type of chemical bond using EDA is a questionable task. Besides, we briefly discuss that the widely used EDA pathway, which is merely an arbitrary choice among infinite possible paths, comes to conclusions not consistent with our widely accepted knowledge of bond formation even for the simplest molecules.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

<a href="/cs/project/LM2015085" target="_blank" >LM2015085: CERIT Scientific Cloud</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Rok uplatnění

2020

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Physical Chemistry Chemical Physics

ISSN

1463-9076

e-ISSN

1463-9084

Svazek periodika

22

Číslo periodika v rámci svazku

39

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

6

Strana od-do

22459-22464

Kód UT WoS článku

000581179800028

EID výsledku v databázi Scopus

2-s2.0-85093538498