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Article: The ozone–water complex: CCSD(T)/CBS structures and anharmonic vibrational spectroscopy of O3(H2O)n, (n = 1 − 2)
| Title | The ozone–water complex: CCSD(T)/CBS structures and anharmonic vibrational spectroscopy of O3(H2O)<i>n</i>, (<i>n</i> = 1 − 2) |
|---|---|
| Authors | |
| Issue Date | 24-Aug-2020 |
| Publisher | American Institute of Physics |
| Citation | The Journal of Chemical Physics, 2020, v. 153, n. 8 How to Cite? |
| Abstract | Ozone–water complexes O3(H2O)n (n = 1–2) have been studied using coupled cluster theory with triple excitations CCSD(T) with correlation consistent basis sets aug-cc-pVnZ (n = D, T, Q) and complete basis set (CBS) extrapolation techniques. We identified seven dimer (n = 1) and nine trimer species (n = 2) with open C2v and cyclic D3h ozone. Calculations at the CCSD(T)/CBS level of theory for C2v O3(H2O) on the counterpoise (CP)-corrected potential energy surface yield a dissociation energy of De = 2.31 kcal/mol and an O3 central-oxygen (Oc) H2O oxygen (Ow) distance r[Oc⋯Ow] of 3.097 Å, which is in good agreement with an experimental value of 2.957 Å [J. Z. Gillies et al., J. Mol. Spectrosc. 146, 493 (1991)]. Combining our CCSD(T)/CBS value of De for C2v O3(H2O) with our best estimate anharmonic CCSD(T)/aVTZ ΔZPE yields a Do value of 1.82 kcal/mol; the CCSD(T)/CBS value of De for D3h O3(H2O) is 1.51 kcal/mol and yields an anharmonic CCSD(T)/aVTZ Do = 0.99 kcal/mol. CCSD(T)/aVTZ dissociation energies and structures for C2v O3(H2O)2 are De = 4.15 kcal/mol, (Do = 3.08 kcal/mol) and r[Oc⋯Ow] = 2.973 Å, and De = 2.64 kcal/mol (Do = 1.68 kcal/mol) with r[Oc⋯Ow] = 2.828 Å for D3h O3(H2O)2. The results from ab initio molecular dynamics simulations, which consider dynamic and thermal effects in O3(H2O), show that the O3(H2O) complex remains stable at 50 K and dynamically interconverts between two hydrogen-bonded conformers with short Oc⋯Ow contacts (3.85 Å). Carr–Parrinello molecular dynamic (CPMD) simulations for O3(H2O) and O3(H2O)2 at 100 K demonstrate that O3(H2O)2 remains structurally intact, whereas O3(H2O) dissociates to free ozone and water, a feature consistent with the larger average binding energy in O3(H2O)2 (2.2 kcal/mol) vs that in O3(H2O) (1.8 kcal/mol). Finally, the results from CCSD(T)/CBS and CPMD simulations demonstrate that the large inter-trimer binding energies in O3(H2O)2 would give rise to an elevated trimer/dimer population ratio, making O3(H2O)2 a particularly stable and spectroscopically detectable complex. |
| Persistent Identifier | http://hdl.handle.net/10722/337499 |
| ISSN | 2023 Impact Factor: 3.1 2023 SCImago Journal Rankings: 1.101 |
| ISI Accession Number ID |
| DC Field | Value | Language |
|---|---|---|
| dc.contributor.author | Hui, Wallace C H | - |
| dc.contributor.author | Lemke, Kono H | - |
| dc.date.accessioned | 2024-03-11T10:21:22Z | - |
| dc.date.available | 2024-03-11T10:21:22Z | - |
| dc.date.issued | 2020-08-24 | - |
| dc.identifier.citation | The Journal of Chemical Physics, 2020, v. 153, n. 8 | - |
| dc.identifier.issn | 0021-9606 | - |
| dc.identifier.uri | http://hdl.handle.net/10722/337499 | - |
| dc.description.abstract | <p>Ozone–water complexes O<sub>3</sub>(H<sub>2</sub>O)<sub><em>n</em></sub> (<em>n</em> = 1–2) have been studied using coupled cluster theory with triple excitations CCSD(T) with correlation consistent basis sets aug-cc-pV<em>n</em>Z (<em>n</em> = D, T, Q) and complete basis set (CBS) extrapolation techniques. We identified seven dimer (<em>n</em> = 1) and nine trimer species (<em>n</em> = 2) with open C<sub>2<em>v</em></sub> and cyclic D<sub>3<em>h</em></sub> ozone. Calculations at the CCSD(T)/CBS level of theory for C<sub>2<em>v</em></sub> O<sub>3</sub>(H<sub>2</sub>O) on the counterpoise (CP)-corrected potential energy surface yield a dissociation energy of D<sub><em>e</em></sub> = 2.31 kcal/mol and an O<sub>3</sub> central-oxygen (O<sub><em>c</em></sub>) H<sub>2</sub>O oxygen (O<sub><em>w</em></sub>) distance <em>r</em>[O<sub><em>c</em></sub>⋯O<sub><em>w</em></sub>] of 3.097 Å, which is in good agreement with an experimental value of 2.957 Å [J. Z. Gillies <em>et al.</em>, J. Mol. Spectrosc. <strong>146</strong>, 493 (1991)]. Combining our CCSD(T)/CBS value of D<sub><em>e</em></sub> for C<sub>2<em>v</em></sub> O<sub>3</sub>(H<sub>2</sub>O) with our best estimate anharmonic CCSD(T)/aVTZ ΔZPE yields a D<sub>o</sub> value of 1.82 kcal/mol; the CCSD(T)/CBS value of D<sub><em>e</em></sub> for D<sub>3<em>h</em></sub> O<sub>3</sub>(H<sub>2</sub>O) is 1.51 kcal/mol and yields an anharmonic CCSD(T)/aVTZ D<sub>o</sub> = 0.99 kcal/mol. CCSD(T)/aVTZ dissociation energies and structures for C<sub>2<em>v</em></sub> O<sub>3</sub>(H<sub>2</sub>O)<sub>2</sub> are D<sub><em>e</em></sub> = 4.15 kcal/mol, (D<sub>o</sub> = 3.08 kcal/mol) and <em>r</em>[O<sub><em>c</em></sub>⋯O<sub><em>w</em></sub>] = 2.973 Å, and D<sub><em>e</em></sub> = 2.64 kcal/mol (D<sub>o</sub> = 1.68 kcal/mol) with <em>r</em>[O<sub><em>c</em></sub>⋯O<sub><em>w</em></sub>] = 2.828 Å for D<sub>3<em>h</em></sub> O<sub>3</sub>(H<sub>2</sub>O)<sub>2</sub>. The results from <em>ab initio</em> molecular dynamics simulations, which consider dynamic and thermal effects in O<sub>3</sub>(H<sub>2</sub>O), show that the O<sub>3</sub>(H<sub>2</sub>O) complex remains stable at 50 K and dynamically interconverts between two hydrogen-bonded conformers with short O<sub><em>c</em></sub>⋯O<sub><em>w</em></sub> contacts (3.85 Å). Carr–Parrinello molecular dynamic (CPMD) simulations for O<sub>3</sub>(H<sub>2</sub>O) and O<sub>3</sub>(H<sub>2</sub>O)<sub>2</sub> at 100 K demonstrate that O<sub>3</sub>(H<sub>2</sub>O)<sub>2</sub> remains structurally intact, whereas O<sub>3</sub>(H<sub>2</sub>O) dissociates to free ozone and water, a feature consistent with the larger average binding energy in O<sub>3</sub>(H<sub>2</sub>O)<sub>2</sub> (2.2 kcal/mol) vs that in O<sub>3</sub>(H<sub>2</sub>O) (1.8 kcal/mol). Finally, the results from CCSD(T)/CBS and CPMD simulations demonstrate that the large inter-trimer binding energies in O<sub>3</sub>(H<sub>2</sub>O)<sub>2</sub> would give rise to an elevated trimer/dimer population ratio, making O<sub>3</sub>(H<sub>2</sub>O)<sub>2</sub> a particularly stable and spectroscopically detectable complex.</p> | - |
| dc.language | eng | - |
| dc.publisher | American Institute of Physics | - |
| dc.relation.ispartof | The Journal of Chemical Physics | - |
| dc.title | The ozone–water complex: CCSD(T)/CBS structures and anharmonic vibrational spectroscopy of O3(H2O)<i>n</i>, (<i>n</i> = 1 − 2) | - |
| dc.type | Article | - |
| dc.identifier.doi | 10.1063/5.0015597 | - |
| dc.identifier.scopus | eid_2-s2.0-85090089441 | - |
| dc.identifier.volume | 153 | - |
| dc.identifier.issue | 8 | - |
| dc.identifier.eissn | 1089-7690 | - |
| dc.identifier.isi | WOS:000565328400002 | - |
| dc.identifier.issnl | 0021-9606 | - |