A Many-Body Perspective of Nuclear Quantum Effects in Aqueous Clusters.
| Autor: | Lambros E; Department of Chemistry, University of Washington, Seattle, Washington 98195, United States., Fetherolf JH; Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States., Hammes-Schiffer S; Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States., Li X; Department of Chemistry, University of Washington, Seattle, Washington 98195, United States. |
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| Jazyk: | angličtina |
| Zdroj: | The journal of physical chemistry letters [J Phys Chem Lett] 2024 Apr 18; Vol. 15 (15), pp. 4070-4075. Date of Electronic Publication: 2024 Apr 08. |
| DOI: | 10.1021/acs.jpclett.4c00439 |
| Abstrakt: | Nuclear quantum effects play an important role in the structure and thermodynamics of aqueous systems. By performing a many-body expansion with nuclear-electronic orbital (NEO) theory, we show that proton quantization can give rise to significant energetic contributions for many-body interactions spanning several molecules in single-point energy calculations of water clusters. Although zero-point motion produces a large increase in energy at the one-body level, nuclear quantum effects serve to stabilize higher-order molecular interactions. These results are significant because they demonstrate that nuclear quantum effects play a nontrivial role in many-body interactions of aqueous systems. Our approach also provides a pathway for incorporating nuclear quantum effects into water potential energy surfaces. The NEO approach is advantageous for many-body expansion analyses because it includes nuclear quantum effects directly in the energies. |
| Databáze: | MEDLINE |
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