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Article: Structure and binding energy of the H2S dimer at the CCSD(T) complete basis set limit
Title | Structure and binding energy of the H2S dimer at the CCSD(T) complete basis set limit |
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Authors | |
Issue Date | 2017 |
Publisher | American Institute of Physics. The Journal's web site is located at http://jcp.aip.org/jcp/staff.jsp |
Citation | Journal of Chemical Physics, 2017, v. 146 n. 23, article no. 234301, p. 1-11 How to Cite? |
Abstract | This study presents results for the binding energy and geometry of the H2S dimer which have been computed using Møller-Plesset perturbation theory (MP2, MP4) and coupled cluster (CCSD, CCSD(T)) calculations with basis sets up to aug-cc-pV5Z. Estimates of De, EZPE, Do, and dimer geometry have been obtained at each level of theory by taking advantage of the systematic convergence behavior toward the complete basis set (CBS) limit. The CBS limit binding energy values of De are 1.91 (MP2), 1.75 (MP4), 1.41 (CCSD), and 1.69 kcal/mol (CCSD[T]). The most accurate values for the equilibrium S-S distance rSS (without counterpoise correction) are 4.080 (MP2/aug-cc-pV5Z), 4.131 (MP4/aug-cc-pVQZ), 4.225 (CCSD/aug-cc-pVQZ), and 4.146 Å (CCSD(T)/aug-cc-pVQZ). This study also evaluates the effect of counterpoise correction on the H2S dimer geometry and binding energy. As regards the structure of (H2S)2, MPn, CCSD, and CCSD(T) level values of rSS, obtained by performing geometry optimizations on the counterpoise-corrected potential energy surface, converge systematically to CBS limit values of 4.099 (MP2), 4.146 (MP4), 4.233 (CCSD), and 4.167 Å (CCSD(T)). The corresponding CBS limit values of the equilibrium binding energy De are 1.88 (MP2), 1.76 (MP4), 1.41 (CCSD), and 1.69 kcal/mol (CCSD(T)), the latter in excellent agreement with the measured binding energy value of 1.68 ± 0.02 kcal/mol reported by Ciaffoni et al. [Appl. Phys. B 92, 627 (2008)]. Combining CBS electronic binding energies De with EZPE predicted by CCSD(T) vibrational second-order perturbation theory calculations yields Do = 1.08 kcal/mol, which is around 0.6 kcal/mol smaller than the measured value of 1.7 ± 0.3 kcal/mol. Overall, the results presented here demonstrate that the application of high level calculations, in particular CCSD(T), in combination with augmented correlation consistent basis sets provides valuable insight into the structure and energetics of the hydrogen sulfide dimer. |
Persistent Identifier | http://hdl.handle.net/10722/247353 |
ISSN | 2023 Impact Factor: 3.1 2023 SCImago Journal Rankings: 1.101 |
ISI Accession Number ID |
DC Field | Value | Language |
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dc.contributor.author | Lemke, KH | - |
dc.date.accessioned | 2017-10-18T08:26:00Z | - |
dc.date.available | 2017-10-18T08:26:00Z | - |
dc.date.issued | 2017 | - |
dc.identifier.citation | Journal of Chemical Physics, 2017, v. 146 n. 23, article no. 234301, p. 1-11 | - |
dc.identifier.issn | 0021-9606 | - |
dc.identifier.uri | http://hdl.handle.net/10722/247353 | - |
dc.description.abstract | This study presents results for the binding energy and geometry of the H2S dimer which have been computed using Møller-Plesset perturbation theory (MP2, MP4) and coupled cluster (CCSD, CCSD(T)) calculations with basis sets up to aug-cc-pV5Z. Estimates of De, EZPE, Do, and dimer geometry have been obtained at each level of theory by taking advantage of the systematic convergence behavior toward the complete basis set (CBS) limit. The CBS limit binding energy values of De are 1.91 (MP2), 1.75 (MP4), 1.41 (CCSD), and 1.69 kcal/mol (CCSD[T]). The most accurate values for the equilibrium S-S distance rSS (without counterpoise correction) are 4.080 (MP2/aug-cc-pV5Z), 4.131 (MP4/aug-cc-pVQZ), 4.225 (CCSD/aug-cc-pVQZ), and 4.146 Å (CCSD(T)/aug-cc-pVQZ). This study also evaluates the effect of counterpoise correction on the H2S dimer geometry and binding energy. As regards the structure of (H2S)2, MPn, CCSD, and CCSD(T) level values of rSS, obtained by performing geometry optimizations on the counterpoise-corrected potential energy surface, converge systematically to CBS limit values of 4.099 (MP2), 4.146 (MP4), 4.233 (CCSD), and 4.167 Å (CCSD(T)). The corresponding CBS limit values of the equilibrium binding energy De are 1.88 (MP2), 1.76 (MP4), 1.41 (CCSD), and 1.69 kcal/mol (CCSD(T)), the latter in excellent agreement with the measured binding energy value of 1.68 ± 0.02 kcal/mol reported by Ciaffoni et al. [Appl. Phys. B 92, 627 (2008)]. Combining CBS electronic binding energies De with EZPE predicted by CCSD(T) vibrational second-order perturbation theory calculations yields Do = 1.08 kcal/mol, which is around 0.6 kcal/mol smaller than the measured value of 1.7 ± 0.3 kcal/mol. Overall, the results presented here demonstrate that the application of high level calculations, in particular CCSD(T), in combination with augmented correlation consistent basis sets provides valuable insight into the structure and energetics of the hydrogen sulfide dimer. | - |
dc.language | eng | - |
dc.publisher | American Institute of Physics. The Journal's web site is located at http://jcp.aip.org/jcp/staff.jsp | - |
dc.relation.ispartof | Journal of Chemical Physics | - |
dc.rights | This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing. This article appeared in Journal of Chemical Physics, 2017, v. 146 n. 23, article no. 234301, p. 1-11 and may be found at https://doi.org/10.1063/1.4985094 | - |
dc.title | Structure and binding energy of the H2S dimer at the CCSD(T) complete basis set limit | - |
dc.type | Article | - |
dc.identifier.email | Lemke, KH: kono@hku.hk | - |
dc.identifier.authority | Lemke, KH=rp00729 | - |
dc.description.nature | published_or_final_version | - |
dc.identifier.doi | 10.1063/1.4985094 | - |
dc.identifier.scopus | eid_2-s2.0-85020503244 | - |
dc.identifier.hkuros | 280923 | - |
dc.identifier.volume | 146 | - |
dc.identifier.issue | 23 | - |
dc.identifier.spage | article no. 234301, p. 1 | - |
dc.identifier.epage | article no. 234301, p. 11 | - |
dc.identifier.isi | WOS:000403376600001 | - |
dc.publisher.place | United States | - |
dc.identifier.issnl | 0021-9606 | - |