Vladimir Fishman, Emmanouil Semidalas, Margarita Shepelenko, Jan M. L. Martin
{"title":"基集叠加误差显著影响后CCSD(T)校正吗？","authors":"Vladimir Fishman, Emmanouil Semidalas, Margarita Shepelenko, Jan M. L. Martin","doi":"10.1002/jcc.70007","DOIUrl":null,"url":null,"abstract":"<p>We have investigated the title question for both a subset of the W4-11 total atomization energies benchmark, and for the A24x8 noncovalent interactions benchmark. Overall, counterpoise corrections to post-CCSD(<i>T</i>) contributions are about two orders of magnitude less important than those to the CCSD(<i>T</i>) interaction energy. Counterpoise corrections for connected quadruple substitutions (<i>Q</i>) are negligible, and <span></span><math>\n <semantics>\n <mrow>\n <msub>\n <mfenced>\n <mi>Q</mi>\n </mfenced>\n <mi>Λ</mi>\n </msub>\n <mo>−</mo>\n <mfenced>\n <mi>Q</mi>\n </mfenced>\n </mrow>\n <annotation>$$ {(Q)}_{\\Lambda}-(Q) $$</annotation>\n </semantics></math> or <span></span><math>\n <semantics>\n <mrow>\n <msub>\n <mi>T</mi>\n <mn>4</mn>\n </msub>\n <mo>−</mo>\n <mfenced>\n <mi>Q</mi>\n </mfenced>\n </mrow>\n <annotation>$$ {T}_4-(Q) $$</annotation>\n </semantics></math> especially so. In contrast, for atomization energies, the <span></span><math>\n <semantics>\n <mrow>\n <msub>\n <mi>T</mi>\n <mn>3</mn>\n </msub>\n <mo>−</mo>\n <mfenced>\n <mi>T</mi>\n </mfenced>\n </mrow>\n <annotation>$$ {T}_3-(T) $$</annotation>\n </semantics></math> counterpoise correction can reach about 0.05 kcal/mol for small basis sets like cc-pVDZ, thought it rapidly tapers off with cc-pVTZ and especially aug-cc-pVTZ basis sets. It is reduced to insignificance by the extrapolation of <span></span><math>\n <semantics>\n <mrow>\n <msub>\n <mi>T</mi>\n <mn>3</mn>\n </msub>\n <mo>−</mo>\n <mfenced>\n <mi>T</mi>\n </mfenced>\n </mrow>\n <annotation>$$ {T}_3-(T) $$</annotation>\n </semantics></math> applied in both W4 and HEAT thermochemistry protocols. In noncovalent dimers, the differential BSSE on post-CCSD(<i>T</i>) correlation contributions is negligible even in basis sets as small as the unpolarized split-valence cc-pVDZ(no d).</p>","PeriodicalId":188,"journal":{"name":"Journal of Computational Chemistry","volume":"46 1","pages":""},"PeriodicalIF":3.4000,"publicationDate":"2024-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/jcc.70007","citationCount":"0","resultStr":"{\"title\":\"Does Basis Set Superposition Error Significantly Affect Post-CCSD(T) Corrections?\",\"authors\":\"Vladimir Fishman, Emmanouil Semidalas, Margarita Shepelenko, Jan M. L. Martin\",\"doi\":\"10.1002/jcc.70007\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>We have investigated the title question for both a subset of the W4-11 total atomization energies benchmark, and for the A24x8 noncovalent interactions benchmark. Overall, counterpoise corrections to post-CCSD(<i>T</i>) contributions are about two orders of magnitude less important than those to the CCSD(<i>T</i>) interaction energy. Counterpoise corrections for connected quadruple substitutions (<i>Q</i>) are negligible, and <span></span><math>\\n <semantics>\\n <mrow>\\n <msub>\\n <mfenced>\\n <mi>Q</mi>\\n </mfenced>\\n <mi>Λ</mi>\\n </msub>\\n <mo>−</mo>\\n <mfenced>\\n <mi>Q</mi>\\n </mfenced>\\n </mrow>\\n <annotation>$$ {(Q)}_{\\\\Lambda}-(Q) $$</annotation>\\n </semantics></math> or <span></span><math>\\n <semantics>\\n <mrow>\\n <msub>\\n <mi>T</mi>\\n <mn>4</mn>\\n </msub>\\n <mo>−</mo>\\n <mfenced>\\n <mi>Q</mi>\\n </mfenced>\\n </mrow>\\n <annotation>$$ {T}_4-(Q) $$</annotation>\\n </semantics></math> especially so. In contrast, for atomization energies, the <span></span><math>\\n <semantics>\\n <mrow>\\n <msub>\\n <mi>T</mi>\\n <mn>3</mn>\\n </msub>\\n <mo>−</mo>\\n <mfenced>\\n <mi>T</mi>\\n </mfenced>\\n </mrow>\\n <annotation>$$ {T}_3-(T) $$</annotation>\\n </semantics></math> counterpoise correction can reach about 0.05 kcal/mol for small basis sets like cc-pVDZ, thought it rapidly tapers off with cc-pVTZ and especially aug-cc-pVTZ basis sets. It is reduced to insignificance by the extrapolation of <span></span><math>\\n <semantics>\\n <mrow>\\n <msub>\\n <mi>T</mi>\\n <mn>3</mn>\\n </msub>\\n <mo>−</mo>\\n <mfenced>\\n <mi>T</mi>\\n </mfenced>\\n </mrow>\\n <annotation>$$ {T}_3-(T) $$</annotation>\\n </semantics></math> applied in both W4 and HEAT thermochemistry protocols. In noncovalent dimers, the differential BSSE on post-CCSD(<i>T</i>) correlation contributions is negligible even in basis sets as small as the unpolarized split-valence cc-pVDZ(no d).</p>\",\"PeriodicalId\":188,\"journal\":{\"name\":\"Journal of Computational Chemistry\",\"volume\":\"46 1\",\"pages\":\"\"},\"PeriodicalIF\":3.4000,\"publicationDate\":\"2024-12-24\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://onlinelibrary.wiley.com/doi/epdf/10.1002/jcc.70007\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Computational Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://onlinelibrary.wiley.com/doi/10.1002/jcc.70007\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Computational Chemistry","FirstCategoryId":"92","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/jcc.70007","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Does Basis Set Superposition Error Significantly Affect Post-CCSD(T) Corrections?
We have investigated the title question for both a subset of the W4-11 total atomization energies benchmark, and for the A24x8 noncovalent interactions benchmark. Overall, counterpoise corrections to post-CCSD(T) contributions are about two orders of magnitude less important than those to the CCSD(T) interaction energy. Counterpoise corrections for connected quadruple substitutions (Q) are negligible, and or especially so. In contrast, for atomization energies, the counterpoise correction can reach about 0.05 kcal/mol for small basis sets like cc-pVDZ, thought it rapidly tapers off with cc-pVTZ and especially aug-cc-pVTZ basis sets. It is reduced to insignificance by the extrapolation of applied in both W4 and HEAT thermochemistry protocols. In noncovalent dimers, the differential BSSE on post-CCSD(T) correlation contributions is negligible even in basis sets as small as the unpolarized split-valence cc-pVDZ(no d).
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This distinguished journal publishes articles concerned with all aspects of computational chemistry: analytical, biological, inorganic, organic, physical, and materials. The Journal of Computational Chemistry presents original research, contemporary developments in theory and methodology, and state-of-the-art applications. Computational areas that are featured in the journal include ab initio and semiempirical quantum mechanics, density functional theory, molecular mechanics, molecular dynamics, statistical mechanics, cheminformatics, biomolecular structure prediction, molecular design, and bioinformatics.
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