Multiply Charged Anions, Maximum Charge Acceptance, and Higher Electron Affinities of Molecules, Superatoms, and Clusters

Citation: VON SZENTPÁLY László. Multiply Charged Anions, Maximum Charge Acceptance, and Higher Electron Affinities of Molecules, Superatoms, and Clusters[J]. Acta Physico-Chimica Sinica, 2018, 34(6): 675-682. doi: 10.3866/PKU.WHXB201801021 shu

Multiply Charged Anions, Maximum Charge Acceptance, and Higher Electron Affinities of Molecules, Superatoms, and Clusters

VON SZENTPÁLYLászló ^,

.
Institut für Theoretische Chemie, Universität Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, Germany

通讯作者: VON SZENTPÁLYLászló, lszentpaly@yahoo.com

摘要: The addition of electrons to form gas-phase multiply charged anions (MCAs) normally requires sophisticated experiments or calculations.In this work, the factors stabilizing the MCAs, the maximum electron uptake of gas-phase molecules, X, and the electronic stability of MCAs X^Q^-, are discussed. The drawbacks encountered when applying computational and/or conceptual density functional theory (DFT) to MCAs are highlighted. We develop and test a different model based on the valence-state concept. As in DFT, the electronic energy, E(N, v_ex), is a continuous function of the average electron number, N, and the external potential, v_ex, of the nuclei. The valence-state-parabola is a second-order polynomial that allows extending E(N, v_ex) to dianions and higher MCAs. The model expresses the maximum electron acceptance, Q_max, and the higher electron affinities, A_Q, as simple functions of the first electron affinity, A₁, and the ionization energy, I, of the “ancestor” system. Thus, the maximum electron acceptance is Q_{max, calc} = 1 + 12A₁/7(I -A₁). The ground-state parabola model of the conceptual DFT yields approximately half of this value, and it is termed Q_{max, GS} = ${}^{1}\!\!\diagup\!\!{}_{2}\; $ + A₁/(I -A₁). A large variety of molecules are evaluated including fullerenes, metal clusters, super-pnictogens, super-halogens (OF₃), super-alkali species (OLi₃), and neutral or charged transition-metal complexes, AB_mL_n^0/+/-. The calculated second electron affinity A_{2, calc} = A₁-(7/12)(I -A₁) is linearly correlated to the literature references A_{2, lit} with a correlation coefficient R = 0.998. A₂ or A₃ values are predicted for further 24 species. The appearance sizes, n_ap^3-, of triply charged anionic clusters and fullerenes are calculated in agreement with the literature.

关键词:

English

Multiply Charged Anions, Maximum Charge Acceptance, and Higher Electron Affinities of Molecules, Superatoms, and Clusters

VON SZENTPÁLY László ^,

Institut für Theoretische Chemie, Universität Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, Germany

Corresponding author: VON SZENTPÁLY László, lszentpaly@yahoo.com

Received Date: 30 October 2017
Accepted Date: 25 December 2017
Revised Date: 25 December 2017
Available Online: 15 June 2018

Abstract: The addition of electrons to form gas-phase multiply charged anions (MCAs) normally requires sophisticated experiments or calculations.In this work, the factors stabilizing the MCAs, the maximum electron uptake of gas-phase molecules, X, and the electronic stability of MCAs X^Q^-, are discussed. The drawbacks encountered when applying computational and/or conceptual density functional theory (DFT) to MCAs are highlighted. We develop and test a different model based on the valence-state concept. As in DFT, the electronic energy, E(N, v_ex), is a continuous function of the average electron number, N, and the external potential, v_ex, of the nuclei. The valence-state-parabola is a second-order polynomial that allows extending E(N, v_ex) to dianions and higher MCAs. The model expresses the maximum electron acceptance, Q_max, and the higher electron affinities, A_Q, as simple functions of the first electron affinity, A₁, and the ionization energy, I, of the "ancestor" system. Thus, the maximum electron acceptance is Q_{max, calc} = 1 + 12A₁/7(I -A₁). The ground-state parabola model of the conceptual DFT yields approximately half of this value, and it is termed Q_{max, GS} = ${}^{1}\!\!\diagup\!\!{}_{2}\; $ + A₁/(I -A₁). A large variety of molecules are evaluated including fullerenes, metal clusters, super-pnictogens, super-halogens (OF₃), super-alkali species (OLi₃), and neutral or charged transition-metal complexes, AB_mL_n^0/+/-. The calculated second electron affinity A_{2, calc} = A₁-(7/12)(I -A₁) is linearly correlated to the literature references A_{2, lit} with a correlation coefficient R = 0.998. A₂ or A₃ values are predicted for further 24 species. The appearance sizes, n_ap^3-, of triply charged anionic clusters and fullerenes are calculated in agreement with the literature.

Key words:

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Multiply Charged Anions, Maximum Charge Acceptance, and Higher Electron Affinities of Molecules, Superatoms, and Clusters

通讯作者: VON SZENTPÁLYLászló, lszentpaly@yahoo.com

English

Multiply Charged Anions, Maximum Charge Acceptance, and Higher Electron Affinities of Molecules, Superatoms, and Clusters

Corresponding author: VON SZENTPÁLY László, lszentpaly@yahoo.com

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

Multiply Charged Anions, Maximum Charge Acceptance, and Higher Electron Affinities of Molecules, Superatoms, and Clusters

通讯作者: VON SZENTPÁLYLászló, lszentpaly@yahoo.com

English

Multiply Charged Anions, Maximum Charge Acceptance, and Higher Electron Affinities of Molecules, Superatoms, and Clusters

Corresponding author: VON SZENTPÁLY László, lszentpaly@yahoo.com

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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