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Photoionization, Structures, and Energetics of Na-Doped Formic Acid-Water Clusters.

ABSTRACT: The influence of formic acid on water cluster aggregation has been investigated experimentally by mass spectrometry and tunable UV laser ionization applied to Na-doped clusters formed in the supersonic expansion of water vapors seeded with formic acid (FA) as well as theoretically using high level quantum chemistry methods. The mass spectra of Na-FA(H₂ O)_n clusters show an enlarging of mass distribution toward heavier clusters with respect to the Na-(H₂ O)_n clusters, suggesting similar mass distribution in neutral clusters and an influence of formic acid in water aggregation. Density functional theory and coupled-cluster type (DLPNO-CCSD(T)) calculations have been used to calculate structures and energetics of neutral and ionized Na-FA(H₂ O)_n as well as neutral FA(H₂ O)_n . Na-doped clusters are characterized by very stable geometries. The theoretical adiabatic ionization potential values match pretty well the measured appearance energies and the calculated first six electronic excited states show Rydberg-type characters, indicating possible autoionization contributions in the mass spectra. Finally, theoretical calculations on neutral FA(H₂ O)_n clusters show the possibility of similarly stable structures in small clusters containing up to n=4-5 water molecules, where FA interacts significantly with waters. This suggests that FA can compete with water molecules in the starting stage of the aggregation process, by forming stable nucleation seed.

SUBMITTER: Bende A

PROVIDER: S-EPMC9303463 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:ContextMicro-hydration of the aminobenzoic acid is essential to understand its interaction with surrounding water molecules. Understanding the micro-hydration of the aminobenzoic acid is also essential to study its remediation from wastewater. Therefore, we explored the potential energy surfaces (PESs) of the para-aminobenzoic acid-water clusters, ABW[Formula: see text], [Formula: see text], to study the microsolvation of the aminobenzoic acid in water. In addition, we performed a quantum theory of atoms in molecules (QTAIM) analysis to identify the nature of non-covalent bondings in the aminobenzoic acid-water clusters. Furthermore, temperature effects on the stability of the located isomers have been examined. The located structures have been used to calculate the hydration free energy and the hydration enthalpy of the aminobenzoic acid using the cluster continuum solvation model. The hydration free energy and the hydration enthalpy of the aminobenzoic acid at room temperature are evaluated to be -7.0 kcal/mol and -18.1 kcal/mol, respectively. The hydration enthalpy is in perfect agreement with a previous experimental estimate. Besides, temperature effects on the calculated hydration enthalpy and free energy are reported. Finally, we calculated the gas phase binding energies of the most stable structures of the ABW[Formula: see text] clusters using twelve functionals of density functional theory (DFT), including empirical dispersion. The DFT functionals are benchmarked against the DLPNO-CCSD(T)/CBS. We have found that the three most suitable DFT functionals are classified in the following order: PW6B95D3 > MN15 > [Formula: see text]B97XD. Therefore, the PW6B95D3 functional is recommended for further study of the aminobenzoic acid-water clusters and similar systems.MethodsThe exploration started with classical molecular dynamics simulations followed by complete optimization at the PW6B95D3/def2-TZVP level of theory. Optimizations are performed using Gaussian 16 suite of codes. QTAIM analysis is performed using the AIMAll program.

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Photoionization, Structures, and Energetics of Na-Doped Formic Acid-Water Clusters.

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