The benzoic acid–water complex: a potential atmospheric nucleation precursor studied using microwave spectroscopy and ab initio calculations

Literature Information

Publication Date 2013-11-28
DOI 10.1039/C3CP54486A
Impact Factor 3.676
Authors

Elijah G. Schnitzler, Wolfgang Jäger


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Abstract

The pure rotational, high-resolution spectrum of the benzoic acid–water complex was measured in the range of 4–14 GHz, using a cavity-based molecular beam Fourier-transform microwave spectrometer. In all, 40 a-type transitions and 2 b-type transitions were measured for benzoic acid–water, and 12 a-type transitions were measured for benzoic acid–D2O. The equilibrium geometry of benzoic acid–water was determined with ab initio calculations, at the B3LYP, M06-2X, and MP2 levels of theory, with the 6-311++G(2df,2pd) basis set. The experimental rotational spectrum is most consistent with the B3LYP-predicted geometry. Narrow splittings were observed in the b-type transitions, and possible tunnelling motions were investigated using the B3LYP/6-311++G(d,p) level of theory. Rotation of the water moiety about the lone electron pair hydrogen-bonded to benzoic acid, across a barrier of 7.0 kJ mol−1, is the most likely cause for the splitting. Wagging of the unbound hydrogen atom of water is barrier-less, and this large amplitude motion results in the absence of c-type transitions. The interaction and spectroscopic dissociation energies calculated using B3LYP and MP2 are in good agreement, but those calculated using M06-2X indicate excess stabilization, possibly due to dispersive interactions being over-estimated. The equilibrium constant of hydration was calculated by statistical thermodynamics, using ab initio results and the experimental rotational constants. This allowed us to estimate the changes in percentage of hydrated benzoic acid with variations in the altitude, region, and season. Using monitoring data from Calgary, Alberta, and the MP2-predicted dissociation energy, a yearly average of 1% of benzoic acid is expected to be present in the form of benzoic acid–water. However, this percentage depends sensitively on the dissociation energy. For example, when using the M06-2X-predicted dissociation energy, we find it increases to 18%.

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Front cover

2022-02-01 Cover

DOI: 10.1039/D2QO90008D

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Source Journal

Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
Articles per Year: 3036

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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