Nature of the Three-Electron Bond

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216224%3A14740%2F18%3A00104282" target="_blank" >RIV/00216224:14740/18:00104282 - isvavai.cz</a>

Výsledek na webu

<a href="https://pubs.acs.org/doi/10.1021/acs.jpca.7b11919" target="_blank" >https://pubs.acs.org/doi/10.1021/acs.jpca.7b11919</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.jpca.7b11919" target="_blank" >10.1021/acs.jpca.7b11919</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Nature of the Three-Electron Bond

Popis výsledku v původním jazyce

We analyze the properties of 15 3-electron bonds, which include sigma-3-electron-bonds, such as dihalide radical anions and di-noble gas radical cations, pi-3-electron-bonds as in hydrazine radical cations, and doubly-pi-(3e)-bonded species such as O-2, FeO+, S-2, etc. The primary analytical tool is the breathing-orbital valence-bond (BOVB) method, which enables us to quantify the charge shift resonance energy (RECS) of the three electrons, and the bond dissociation energies (De). BOVB is tested reliable against MRCI calculations. Our findings show that in all 3-electron bonds, none of the VB structures have by themselves any bonding. In fact, in each VB structure, the three electrons maintain Pauli repulsion, while the entire bonding energy arises from resonance due to the charge shift between the two or more constituent VB structures. Hence, 3e-bonds are charge shift bonds (CSBs). The CSB character is probed by calculating the Laplacian (L) of the 3e-bond. Thus, much like the CSBs in electron-pair bonds, such as F-2 or the central bond in [1.1.1]propellane, here too L is positive, thus showing the excess kinetic energy of the shared density due to the Pauli repulsion in the 3-electron VB structures. The RECS values for 3-electron bonds are invariably larger than the corresponding bond energies. For the doubly-pi-(3e) -bonded species, RECS is very large, exceeding 100 kcal mol(-1). As such, it is fitting to conclude that sigma- and pi-3-electron-bonds find their natural place in the CSB family along with two-electron CSBs, with which they share identical energetic and topological characteristics. Experimental manifestations/tests of 3e-CSBs are proposed.

Název v anglickém jazyce

Nature of the Three-Electron Bond

Popis výsledku anglicky

We analyze the properties of 15 3-electron bonds, which include sigma-3-electron-bonds, such as dihalide radical anions and di-noble gas radical cations, pi-3-electron-bonds as in hydrazine radical cations, and doubly-pi-(3e)-bonded species such as O-2, FeO+, S-2, etc. The primary analytical tool is the breathing-orbital valence-bond (BOVB) method, which enables us to quantify the charge shift resonance energy (RECS) of the three electrons, and the bond dissociation energies (De). BOVB is tested reliable against MRCI calculations. Our findings show that in all 3-electron bonds, none of the VB structures have by themselves any bonding. In fact, in each VB structure, the three electrons maintain Pauli repulsion, while the entire bonding energy arises from resonance due to the charge shift between the two or more constituent VB structures. Hence, 3e-bonds are charge shift bonds (CSBs). The CSB character is probed by calculating the Laplacian (L) of the 3e-bond. Thus, much like the CSBs in electron-pair bonds, such as F-2 or the central bond in [1.1.1]propellane, here too L is positive, thus showing the excess kinetic energy of the shared density due to the Pauli repulsion in the 3-electron VB structures. The RECS values for 3-electron bonds are invariably larger than the corresponding bond energies. For the doubly-pi-(3e) -bonded species, RECS is very large, exceeding 100 kcal mol(-1). As such, it is fitting to conclude that sigma- and pi-3-electron-bonds find their natural place in the CSB family along with two-electron CSBs, with which they share identical energetic and topological characteristics. Experimental manifestations/tests of 3e-CSBs are proposed.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

<a href="/cs/project/LQ1601" target="_blank" >LQ1601: CEITEC 2020</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)<br>I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2018

Kód důvěrnosti údajů

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

Název periodika

Journal of Physical Chemistry A

ISSN

1089-5639

e-ISSN

—

Svazek periodika

122

Číslo periodika v rámci svazku

7

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

13

Strana od-do

1873-1885

Kód UT WoS článku

000426221000006

EID výsledku v databázi Scopus

2-s2.0-85042540229