Abstract
We have carried out an extensive exploration of gas-phase alkali metal cation affinities (AMCA) of archetypal anionic bases across the periodic system using relativistic density functional theory at ZORA-BP86/QZ4P//ZORA-BP86/TZ2P. AMCA values of all bases were computed for the lithium, sodium, potassium, rubidium and cesium cations and compared with the corresponding proton affinities (PA). One purpose of this work is to provide an intrinsically consistent set of values of the 298 K AMCAs of all anionic (XHn-1 −) constituted by main group-element hydrides of groups 14–17 along the periods 2–6. In particular, we wish to establish the trend in affinity for a cation as the latter varies from proton to, and along, the alkali cations. Our main purpose is to understand these trends in terms of the underlying bonding mechanism using Kohn–Sham molecular orbital theory together with a quantitative bond energy decomposition analyses (EDA).
| Original language | English |
|---|---|
| Pages (from-to) | 2604-2611 |
| Number of pages | 8 |
| Journal | Chemistry - An Asian Journal |
| Volume | 12 |
| Issue number | 19 |
| DOIs | |
| Publication status | Published - 5 Oct 2017 |
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Keywords
- alkali metal cation affinities
- bond theory
- density functional calculations
- proton affinities
- thermochemistry
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Alkali Metal Cation Affinities of Anionic Main Group-Element Hydrides Across the Periodic Table. / Boughlala, Zakaria; Fonseca Guerra, Célia; Bickelhaupt, F. Matthias.
In: Chemistry - An Asian Journal, Vol. 12, No. 19, 05.10.2017, p. 2604-2611.Research output: Contribution to Journal › Article › Academic › peer-review
TY - JOUR
T1 - Alkali Metal Cation Affinities of Anionic Main Group-Element Hydrides Across the Periodic Table
AU - Boughlala, Zakaria
AU - Fonseca Guerra, Célia
AU - Bickelhaupt, F. Matthias
PY - 2017/10/5
Y1 - 2017/10/5
N2 - We have carried out an extensive exploration of gas-phase alkali metal cation affinities (AMCA) of archetypal anionic bases across the periodic system using relativistic density functional theory at ZORA-BP86/QZ4P//ZORA-BP86/TZ2P. AMCA values of all bases were computed for the lithium, sodium, potassium, rubidium and cesium cations and compared with the corresponding proton affinities (PA). One purpose of this work is to provide an intrinsically consistent set of values of the 298 K AMCAs of all anionic (XHn-1 −) constituted by main group-element hydrides of groups 14–17 along the periods 2–6. In particular, we wish to establish the trend in affinity for a cation as the latter varies from proton to, and along, the alkali cations. Our main purpose is to understand these trends in terms of the underlying bonding mechanism using Kohn–Sham molecular orbital theory together with a quantitative bond energy decomposition analyses (EDA).
AB - We have carried out an extensive exploration of gas-phase alkali metal cation affinities (AMCA) of archetypal anionic bases across the periodic system using relativistic density functional theory at ZORA-BP86/QZ4P//ZORA-BP86/TZ2P. AMCA values of all bases were computed for the lithium, sodium, potassium, rubidium and cesium cations and compared with the corresponding proton affinities (PA). One purpose of this work is to provide an intrinsically consistent set of values of the 298 K AMCAs of all anionic (XHn-1 −) constituted by main group-element hydrides of groups 14–17 along the periods 2–6. In particular, we wish to establish the trend in affinity for a cation as the latter varies from proton to, and along, the alkali cations. Our main purpose is to understand these trends in terms of the underlying bonding mechanism using Kohn–Sham molecular orbital theory together with a quantitative bond energy decomposition analyses (EDA).
KW - alkali metal cation affinities
KW - bond theory
KW - density functional calculations
KW - proton affinities
KW - thermochemistry
UR - http://www.scopus.com/inward/record.url?scp=85029364413&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85029364413&partnerID=8YFLogxK
U2 - 10.1002/asia.201700956
DO - 10.1002/asia.201700956
M3 - Article
VL - 12
SP - 2604
EP - 2611
JO - Chemistry - An Asian Journal
JF - Chemistry - An Asian Journal
SN - 1861-4728
IS - 19
ER -