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Title: Beyond chemical accuracy in the heavy p-block: The first ionization potentials and electron affinities of Ga-Kr, In-Xe, and Tl-Rn

Abstract

A relativistic coupled-cluster version of the Feller-Peterson-Dixon (FPD) composite method was previously used to accurately calculate the first ionization potentials (IP) and electron affinities (EAs) of the post-d, p-block elements Ga–Rn. Complete basis set (CBS) extrapolations including outer-core correlation at the CCSD(T) level of theory were combined with contributions from higher order electron correlation up to CCSDTQ, quantum electrodynamic effects (Lamb shift), and spin-orbit (SO) coupling including the Gaunt contribution. Several methods for including SO were investigated, in which all involved the four-component (4c) Dirac-Coulomb (DC) Hamiltonian. Here, the treatment of SO coupling was the contribution that limited the final accuracy of the present results. In the cases where 4c-DC-CCSD(T) could be reliably used for the SO contributions, the final composite IPs and EAs agreed with the available experimental values to within an unsigned average error of just 0.16 and 0.20 kcal/mol, respectively. In all cases the final IPs and EAs were within 1 kcal/mol of the available experimental values, except for the EAs of the group 13 elements (Ga, In, Tl), where the currently accepted experimental values appear to be too large by as much as 4 kcal/mol. The values predicted in this work, which have estimated uncertainties ofmore » ±0.5 kcal/mol, are 5.25 (Ga), 7.69 (In), and 7.39 (Tl) kcal/mol. For the EAs of Po and At, which do not have experimental values, the current calculations predict values of 34.2 and 55.8 kcal/mol with estimated uncertainties of ±0.6 and ±0.3 kcal/mol, respectively.« less

Authors:
ORCiD logo [1];  [1]
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  1. Washington State Univ., Pullman, WA (United States)
Publication Date:
Research Org.:
Washington State Univ., Pullman, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1526482
Alternate Identifier(s):
OSTI ID: 1532585; OSTI ID: 1657545
Grant/Contract Number:  
SC0008501
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 151; Journal Issue: 2; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Quantum electrodynamic effects; Spin-orbit interactions; Lamb shift; Coupled-cluster methods; Ions and properties; Correlation-consistent basis sets; Electronic correlation

Citation Formats

Peterson, Kirk A., and Finney, Brian A. Beyond chemical accuracy in the heavy p-block: The first ionization potentials and electron affinities of Ga-Kr, In-Xe, and Tl-Rn. United States: N. p., 2019. Web. doi:10.1063/1.5110174.
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Peterson, Kirk A., & Finney, Brian A. Beyond chemical accuracy in the heavy p-block: The first ionization potentials and electron affinities of Ga-Kr, In-Xe, and Tl-Rn. United States. https://doi.org/10.1063/1.5110174
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Peterson, Kirk A., and Finney, Brian A. Tue . "Beyond chemical accuracy in the heavy p-block: The first ionization potentials and electron affinities of Ga-Kr, In-Xe, and Tl-Rn". United States. https://doi.org/10.1063/1.5110174. https://www.osti.gov/servlets/purl/1526482.
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@article{osti_1526482,
title = {Beyond chemical accuracy in the heavy p-block: The first ionization potentials and electron affinities of Ga-Kr, In-Xe, and Tl-Rn},
author = {Peterson, Kirk A. and Finney, Brian A.},
abstractNote = {A relativistic coupled-cluster version of the Feller-Peterson-Dixon (FPD) composite method was previously used to accurately calculate the first ionization potentials (IP) and electron affinities (EAs) of the post-d, p-block elements Ga–Rn. Complete basis set (CBS) extrapolations including outer-core correlation at the CCSD(T) level of theory were combined with contributions from higher order electron correlation up to CCSDTQ, quantum electrodynamic effects (Lamb shift), and spin-orbit (SO) coupling including the Gaunt contribution. Several methods for including SO were investigated, in which all involved the four-component (4c) Dirac-Coulomb (DC) Hamiltonian. Here, the treatment of SO coupling was the contribution that limited the final accuracy of the present results. In the cases where 4c-DC-CCSD(T) could be reliably used for the SO contributions, the final composite IPs and EAs agreed with the available experimental values to within an unsigned average error of just 0.16 and 0.20 kcal/mol, respectively. In all cases the final IPs and EAs were within 1 kcal/mol of the available experimental values, except for the EAs of the group 13 elements (Ga, In, Tl), where the currently accepted experimental values appear to be too large by as much as 4 kcal/mol. The values predicted in this work, which have estimated uncertainties of ±0.5 kcal/mol, are 5.25 (Ga), 7.69 (In), and 7.39 (Tl) kcal/mol. For the EAs of Po and At, which do not have experimental values, the current calculations predict values of 34.2 and 55.8 kcal/mol with estimated uncertainties of ±0.6 and ±0.3 kcal/mol, respectively.},
doi = {10.1063/1.5110174},
journal = {Journal of Chemical Physics},
number = 2,
volume = 151,
place = {United States},
year = {2019},
month = {7}
}
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Figures / Tables:

Table I Table I: Calculated Gaunt and spin-orbit contributions to the ionization potentials (kcal/mol).
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    Electron affinity of gallium and fine structure of Ga − : Experiment and theory
    journal, November 2019

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