Dataset Information

Alkali Metal Cation Affinities of Neutral Maingroup-Element Hydrides across the Periodic Table.

ABSTRACT: We have carried out an extensive quantum chemical exploration of gas-phase alkali metal cation affinities (AMCAs) of archetypal neutral bases across the periodic system using relativistic density functional theory. One objective of this work is to provide an intrinsically consistent set of values of the 298 K AMCAs of all neutral maingroup-element hydrides XHn of groups 15-18 along the periods 1-6. Our main purpose is to understand these trends in terms of the underlying bonding mechanism using Kohn-Sham molecular orbital theory together with a canonical energy decomposition analysis (EDA). We compare the trends in XHn AMCAs with the trends in XHn proton affinities (PAs). We also examine the differences between the trends in AMCAs of the neutral XHn bases with those in the corresponding anionic XHn-1- bases. Furthermore, we analyze how the cation affinity of our neutral Lewis bases changes along the group-1 cations H+, Li+, Na+, K+, Rb+, and Cs+.

SUBMITTER: Boughlala Z

PROVIDER: S-EPMC6816011 | biostudies-literature | 2019 Oct

REPOSITORIES: biostudies-literature

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Alkali Metal Cation Affinities of Neutral Maingroup-Element Hydrides across the Periodic Table.

Boughlala Zakaria Z Fonseca Guerra Célia C Bickelhaupt F Matthias FM

The journal of physical chemistry. A 20190724 42

We have carried out an extensive quantum chemical exploration of gas-phase alkali metal cation affinities (AMCAs) of archetypal neutral bases across the periodic system using relativistic density functional theory. One objective of this work is to provide an intrinsically consistent set of values of the 298 K AMCAs of all neutral maingroup-element hydrides XH<sub><i>n</i></sub> of groups 15-18 along the periods 1-6. Our main purpose is to understand these trends in terms of the underlying bondin ...[more]

PMID: 31294982

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Project description:NO dissociative adsorption onto 3d metal particles M55 (M = Fe, Co, Ni, and Cu) was investigated theoretically using density functional theory computations. A transition state exists at higher energy in the Cu case but at lower energy in the Fe, Co, and Ni cases than the reactant (sum of M55 and NO), indicating that Cu55 is not reactive for NO dissociative adsorption because NO desorption occurs more easily than the N-O bond cleavage in this case, but Fe55, Co55, and Ni55 are reactive because NO desorption needs a larger destabilization energy than the N-O bond cleavage. This result agrees with the experimental findings. The energy of transition state E(TS) becomes higher in the order of Fe < Co < Ni ≪ Cu. Exothermicity E exo (relative energy to the reactant) decreases in the order of Fe > Co > Ni ≫ Cu. These results indicate that the reactivity for NO dissociative adsorption decreases kinetically and thermodynamically in this order. In addition, the E(TS) and E exo values show that 3d metal particles are more reactive than 4d metal particles when a comparison is made in the same group of the periodic table. Charge transfer (CT) from the metal particle to NO increases as the reaction proceeds. The CT quantity to NO at the TS increases in the order of Cu < Ni < Co < Fe, identical to the increasing order of reactivity. The negative charges of the N and O atoms of the product (N and O adsorbed M55) increase in the order of Ni < Co < Cu < Fe, identical to the increasing order of E exo except for the Cu case; in the Cu case, the discrepancy between the order of E exo and those of the N and O negative charges arises from the presence of valence 4s electron of Cu because it suppresses the CT from N and O to Cu55. From these results, one can infer that the d-valence band-top energy of M55 plays an important role in determining the reactivity for NO dissociative adsorption. Truly, the d valence orbital energy decreases in the order of Fe > Co > Ni ≫ Cu and the 3d metal > 4d metal in the same group of the periodic table, which reflects the dependence of reactivity on the metal element position in the periodic table.

Dataset Information

Alkali Metal Cation Affinities of Neutral Maingroup-Element Hydrides across the Periodic Table.

Publications

Alkali Metal Cation Affinities of Neutral Maingroup-Element Hydrides across the Periodic Table.

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