Infrared spectra and isomeric structures of hydroxide ion-water clusters OH- (H2O)1-5: a comparison with H3O (H2O)1-5

The HO − (aq) ion participates in myriad aqueous phase chemical processes of biological and chemical interest. A molecularly valid description of its hydration state, currently poorly understood, is a natural prerequisite to modeling chemical transformations involving HO − (aq). Here it is shown that the statistical mechanical quasichemical theory of solutions predicts that− is the dominant inner shell coordination structure for HO − (aq) under standard conditions. Experimental observations and other theoretical calculations are adduced to support this conclusion. Hydration free energies of neutral combinations of simple cations with HO − (aq) are evaluated and agree well with experimental values.

show abstract

“…2 of [26]. Table 3 shows that the present inner shell computations are in reasonable agreement with experimental results.…”

Section: Discussionsupporting

confidence: 77%

“…The case 3 + 1 refers to the outer-sphere arrangement of the fourth water discussed in the text. Theoretical calculations for comparable structures from [26] at the B3LYP/aug-ccpVDZ level are also shown. The lower energy of the outer shell arrangement of the fourth water was recently confirmed spectroscopically by Johnson and coworkers [29].…”

Section: Discussionmentioning

confidence: 99%

The hydration state of HO−(aq)

Asthagiri

Pratt

Kress

et al. 2003

Chemical Physics Letters

View full text Add to dashboard Cite

show abstract

“…Protonated and deprotonated clusters of water are known to exhibit a wide variety of isomers with increasing size [54]. For brevity, we consider here only clusters of three and four monomers.…”

Section: Small Ionized Water Clustersmentioning

confidence: 99%

Lewis-inspired representation of dissociable water in clusters and Grotthuss chains

et al. 2011

View full text Add to dashboard Cite

Proton transfer to and from water is critical to the function of water in many settings. However, it has been challenging to model. Here, we present proof-of-principle for an efficient yet robust model based on Lewis-inspired submolecular particles with interactions that deviate from Coulombic at short distances to take quantum effects into account. This "LEWIS" model provides excellent correspondence with experimental structures for water molecules and water clusters in their neutral, protonated and deprotonated forms, reasonable values for the proton affinities of water and hydroxide, a good value for the strength of the hydrogen bond in the water dimer, the correct order of magnitude for the stretch and bend force constants of water, and the expected time course for Grotthuss transport in water chains.

show abstract

“…20 Extensive data on the geometry and thermodynamic properties of the solvated OH Ϫ ion are available from calculations ͑see, for example, Refs. 16,17,21,22, and the references to experimental work therein͒. Direct information on the dynamics has only been provided by ab initio molecular-dynamics simulations.…”

mentioning

confidence: 99%

Dynamics of water molecules in an alkaline environment

Nienhuys

Lock

Santen

et al. 2002

The Journal of Chemical Physics

View full text Add to dashboard Cite

We report on a two-color mid-infrared pump-probe spectroscopic study of the dynamics of the OH stretch vibrations of HDO molecules dissolved in a concentrated ͑10 M͒ solution of NaOD in D 2 O. We observe that spectral holes can be created in the broad OH stretch absorption band that change neither position nor width on a picosecond time scale. This behavior differs strongly from that of pure HDO:D 2 O where rapid spectral diffusion ( c Ϸ600 fs) occurs. The long-living inhomogeneity indicates that a concentrated aqueous NaOX (XϭH,D) solution has a very static hydrogen-bond network. The results also show that the absorption band of the OH stretch vibration consists of two separate classes of OH groups with very different vibrational lifetimes. For component I, the lifetime of the OH stretch vibration is ϳ600 fs and increases with OH frequency, which can be explained from the accompanying decrease in the strength of the hydrogen-bond interaction. This component represents HDO molecules of which the OH group is bonded to a D 2 O molecule via a DO-H¯OD 2 hydrogen bond. For component II, the lifetime is ϳ160 fs, and does not show a significant frequency dependence. This component represents HDO molecules that are hydrogen bonded to a D 2 O molecule or an OD Ϫ ion. The short, frequency-independent vibrational lifetime of component II can be explained from the participation of the HDO molecule and its hydrogen-bonded partner in deuteron and/or proton-transfer processes.

show abstract

Infrared spectra and isomeric structures of hydroxide ion-water clusters OH- (H₂O)_1-5: a comparison with H₃O (H₂O)_1-5

Cited by 93 publications

References 46 publications

The hydration state of HO−(aq)

The hydration state of HO−(aq)

Lewis-inspired representation of dissociable water in clusters and Grotthuss chains

Dynamics of water molecules in an alkaline environment

Contact Info

Product

Resources

About