Minimal Optimized Effective Potentials for Density Functional Theory Studies on Excited-State Proton Dissociation
Recently, a new method [P. Partovi-Azar and D. Sebastiani, <i>J. Chem. Phys.</i> 152, 064101 (2020)] was proposed to increase the efficiency of proton transfer energy calculations in density functional theory by using the T<inline-formula><math xmlns="http://www.w3.org/1998...
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MDPI AG
2021-06-01
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| Series: | Micromachines |
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| Online Access: | https://www.mdpi.com/2072-666X/12/6/679 |
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| author | Pouya Partovi-Azar Daniel Sebastiani |
| author_facet | Pouya Partovi-Azar Daniel Sebastiani |
| author_sort | Pouya Partovi-Azar |
| collection | DOAJ |
| description | Recently, a new method [P. Partovi-Azar and D. Sebastiani, <i>J. Chem. Phys.</i> 152, 064101 (2020)] was proposed to increase the efficiency of proton transfer energy calculations in density functional theory by using the T<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>1</mn></msub></semantics></math></inline-formula> state with additional optimized effective potentials instead of calculations at S<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>1</mn></msub></semantics></math></inline-formula>. In this work, we focus on proton transfer from six prototypical photoacids to neighboring water molecules and show that the reference proton dissociation curves obtained at S<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>1</mn></msub></semantics></math></inline-formula> states using time-dependent density functional theory can be reproduced with a reasonable accuracy by performing T<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>1</mn></msub></semantics></math></inline-formula> calculations at density functional theory level with only one additional effective potential for the acidic hydrogens. We also find that the extra effective potentials for the acidic hydrogens neither change the nature of the T<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>1</mn></msub></semantics></math></inline-formula> state nor the structural properties of solvent molecules upon transfer from the acids. The presented method is not only beneficial for theoretical studies on excited state proton transfer, but we believe that it would also be useful for studying other excited state photochemical reactions. |
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| spelling | doaj.art-6c49a0643a7a480f929b12bf27d7ea2e2023-11-21T23:31:36ZengMDPI AGMicromachines2072-666X2021-06-0112667910.3390/mi12060679Minimal Optimized Effective Potentials for Density Functional Theory Studies on Excited-State Proton DissociationPouya Partovi-Azar0Daniel Sebastiani1Institute of Chemistry, Martin-Luther-University Halle-Wittenberg, Von-Danckelmann-Platz 4, 06120 Halle (Saale), GermanyInstitute of Chemistry, Martin-Luther-University Halle-Wittenberg, Von-Danckelmann-Platz 4, 06120 Halle (Saale), GermanyRecently, a new method [P. Partovi-Azar and D. Sebastiani, <i>J. Chem. Phys.</i> 152, 064101 (2020)] was proposed to increase the efficiency of proton transfer energy calculations in density functional theory by using the T<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>1</mn></msub></semantics></math></inline-formula> state with additional optimized effective potentials instead of calculations at S<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>1</mn></msub></semantics></math></inline-formula>. In this work, we focus on proton transfer from six prototypical photoacids to neighboring water molecules and show that the reference proton dissociation curves obtained at S<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>1</mn></msub></semantics></math></inline-formula> states using time-dependent density functional theory can be reproduced with a reasonable accuracy by performing T<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>1</mn></msub></semantics></math></inline-formula> calculations at density functional theory level with only one additional effective potential for the acidic hydrogens. We also find that the extra effective potentials for the acidic hydrogens neither change the nature of the T<inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><msub><mrow></mrow><mn>1</mn></msub></semantics></math></inline-formula> state nor the structural properties of solvent molecules upon transfer from the acids. The presented method is not only beneficial for theoretical studies on excited state proton transfer, but we believe that it would also be useful for studying other excited state photochemical reactions.https://www.mdpi.com/2072-666X/12/6/679density functional theorytime-dependent density functional theoryoptimized effective potentialsexcited statesproton dissociation |
| spellingShingle | Pouya Partovi-Azar Daniel Sebastiani Minimal Optimized Effective Potentials for Density Functional Theory Studies on Excited-State Proton Dissociation Micromachines density functional theory time-dependent density functional theory optimized effective potentials excited states proton dissociation |
| title | Minimal Optimized Effective Potentials for Density Functional Theory Studies on Excited-State Proton Dissociation |
| title_full | Minimal Optimized Effective Potentials for Density Functional Theory Studies on Excited-State Proton Dissociation |
| title_fullStr | Minimal Optimized Effective Potentials for Density Functional Theory Studies on Excited-State Proton Dissociation |
| title_full_unstemmed | Minimal Optimized Effective Potentials for Density Functional Theory Studies on Excited-State Proton Dissociation |
| title_short | Minimal Optimized Effective Potentials for Density Functional Theory Studies on Excited-State Proton Dissociation |
| title_sort | minimal optimized effective potentials for density functional theory studies on excited state proton dissociation |
| topic | density functional theory time-dependent density functional theory optimized effective potentials excited states proton dissociation |
| url | https://www.mdpi.com/2072-666X/12/6/679 |
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