Beyond chemical accuracy in the heavy p-block: The first ionization potentials and electron affinities of Ga–Kr, In–Xe, and Tl–Rn
A relativistic coupled-cluster version of the Feller-Peterson-Dixon composite method has been used to accurately calculate the first ionization potentials (IPs) and electron affinities (EAs) of the post-d, p-block elements Ga–Rn. Complete basis set extrapolations including outer-core correlation at...
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Veröffentlicht in: | The Journal of chemical physics 2019-07, Vol.151 (2), p.024303-024303 |
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description | A relativistic coupled-cluster version of the Feller-Peterson-Dixon composite method has been used to accurately calculate the first ionization potentials (IPs) and electron affinities (EAs) of the post-d, p-block elements Ga–Rn. Complete basis set 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. 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, and 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_str_mv | 10.1063/1.5110174 |
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Complete basis set 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. 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, and 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.</description><identifier>ISSN: 0021-9606</identifier><identifier>EISSN: 1089-7690</identifier><identifier>DOI: 10.1063/1.5110174</identifier><identifier>PMID: 31301726</identifier><identifier>CODEN: JCPSA6</identifier><language>eng</language><publisher>United States: American Institute of Physics</publisher><subject>Affinity ; Correlation-consistent basis sets ; Coupled-cluster methods ; Coupling (molecular) ; Electronic correlation ; Electrons ; Gallium ; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY ; Ionization potentials ; Ions and properties ; Lamb shift ; Mathematical analysis ; Organic chemistry ; Physics ; Quantum electrodynamic effects ; Spin-orbit interactions ; Uncertainty</subject><ispartof>The Journal of chemical physics, 2019-07, Vol.151 (2), p.024303-024303</ispartof><rights>Author(s)</rights><rights>2019 Author(s). 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Complete basis set 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. 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, and 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.</description><subject>Affinity</subject><subject>Correlation-consistent basis sets</subject><subject>Coupled-cluster methods</subject><subject>Coupling (molecular)</subject><subject>Electronic correlation</subject><subject>Electrons</subject><subject>Gallium</subject><subject>INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY</subject><subject>Ionization potentials</subject><subject>Ions and properties</subject><subject>Lamb shift</subject><subject>Mathematical analysis</subject><subject>Organic chemistry</subject><subject>Physics</subject><subject>Quantum electrodynamic effects</subject><subject>Spin-orbit interactions</subject><subject>Uncertainty</subject><issn>0021-9606</issn><issn>1089-7690</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2019</creationdate><recordtype>article</recordtype><recordid>eNp9kc9u1DAQxi0EotvCgRdAFlxa1BTbsZ2EG1SlVFRCQovEzXImjtYlawfbqbScuPEAfcM-CU53AQkJTvNHv_k84w-hJ5ScUCLLl_REUEpoxe-hBSV1U1SyIffRghBGi0YSuYf2Y7wiJDOMP0R7JS3nVC7Qjzdm412HYWXWFvSANcAUNGywdTitDF4Zfb3BY9EOHr68wsvc6m2ICVvv7DedcsCjT8Ylq4eIddYyg4EUcl_3vXU2WROx7_G5vv1-8z4c4wuXk8_m-A5eDrn46B6hB32eN4938QB9enu2PH1XXH44vzh9fVkA5yIVdU1Al6ZrZT6ga0Qj2rqqhYDOVKxrypYLQyVnpNJ11QHtOBHQcAoUyopIWR6gZ1tdH5NVEWwysALvXF5ZUcEkr1mGDrfQGPzXycSk1jaCGQbtjJ-iYkzU8_eRKqPP_0Kv_BRcPmGmOGWsJvOrR1sKgo8xmF6Nwa512ChK1GyhompnYWaf7hSndm263-QvzzLwYgvM298Z8F-1f8LXPvwB1dj15U9blrJj</recordid><startdate>20190714</startdate><enddate>20190714</enddate><creator>Finney, Brian A.</creator><creator>Peterson, Kirk A.</creator><general>American Institute of Physics</general><general>American Institute of Physics (AIP)</general><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>8FD</scope><scope>H8D</scope><scope>L7M</scope><scope>7X8</scope><scope>OIOZB</scope><scope>OTOTI</scope><orcidid>https://orcid.org/0000-0003-3863-1089</orcidid><orcidid>https://orcid.org/0000-0003-4901-3235</orcidid><orcidid>https://orcid.org/0000000349013235</orcidid><orcidid>https://orcid.org/0000000338631089</orcidid></search><sort><creationdate>20190714</creationdate><title>Beyond chemical accuracy in the heavy p-block: The first ionization potentials and electron affinities of Ga–Kr, In–Xe, and Tl–Rn</title><author>Finney, Brian A. ; Peterson, Kirk A.</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c445t-880ca3edb6301d9595b87855cde72d93b45e164207a87dc1d405c941c1c370663</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2019</creationdate><topic>Affinity</topic><topic>Correlation-consistent basis sets</topic><topic>Coupled-cluster methods</topic><topic>Coupling (molecular)</topic><topic>Electronic correlation</topic><topic>Electrons</topic><topic>Gallium</topic><topic>INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY</topic><topic>Ionization potentials</topic><topic>Ions and properties</topic><topic>Lamb shift</topic><topic>Mathematical analysis</topic><topic>Organic chemistry</topic><topic>Physics</topic><topic>Quantum electrodynamic effects</topic><topic>Spin-orbit interactions</topic><topic>Uncertainty</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Finney, Brian A.</creatorcontrib><creatorcontrib>Peterson, Kirk A.</creatorcontrib><creatorcontrib>Washington State Univ., Pullman, WA (United States)</creatorcontrib><collection>PubMed</collection><collection>CrossRef</collection><collection>Technology Research Database</collection><collection>Aerospace Database</collection><collection>Advanced Technologies Database with Aerospace</collection><collection>MEDLINE - Academic</collection><collection>OSTI.GOV - Hybrid</collection><collection>OSTI.GOV</collection><jtitle>The Journal of chemical physics</jtitle></facets><delivery><delcategory>Remote Search Resource</delcategory><fulltext>fulltext</fulltext></delivery><addata><au>Finney, Brian A.</au><au>Peterson, Kirk A.</au><aucorp>Washington State Univ., Pullman, WA (United States)</aucorp><format>journal</format><genre>article</genre><ristype>JOUR</ristype><atitle>Beyond chemical accuracy in the heavy p-block: The first ionization potentials and electron affinities of Ga–Kr, In–Xe, and Tl–Rn</atitle><jtitle>The Journal of chemical physics</jtitle><addtitle>J Chem Phys</addtitle><date>2019-07-14</date><risdate>2019</risdate><volume>151</volume><issue>2</issue><spage>024303</spage><epage>024303</epage><pages>024303-024303</pages><issn>0021-9606</issn><eissn>1089-7690</eissn><coden>JCPSA6</coden><abstract>A relativistic coupled-cluster version of the Feller-Peterson-Dixon composite method has been used to accurately calculate the first ionization potentials (IPs) and electron affinities (EAs) of the post-d, p-block elements Ga–Rn. Complete basis set 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. 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, and 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.</abstract><cop>United States</cop><pub>American Institute of Physics</pub><pmid>31301726</pmid><doi>10.1063/1.5110174</doi><tpages>9</tpages><orcidid>https://orcid.org/0000-0003-3863-1089</orcidid><orcidid>https://orcid.org/0000-0003-4901-3235</orcidid><orcidid>https://orcid.org/0000000349013235</orcidid><orcidid>https://orcid.org/0000000338631089</orcidid><oa>free_for_read</oa></addata></record> |
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subjects | Affinity Correlation-consistent basis sets Coupled-cluster methods Coupling (molecular) Electronic correlation Electrons Gallium INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY Ionization potentials Ions and properties Lamb shift Mathematical analysis Organic chemistry Physics Quantum electrodynamic effects Spin-orbit interactions Uncertainty |
title | Beyond chemical accuracy in the heavy p-block: The first ionization potentials and electron affinities of Ga–Kr, In–Xe, and Tl–Rn |
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