Nonlinear rotational spectroscopy reveals many-body interactions in water molecules

Because of their central importance in chemistry and biology, water molecules have been the subject of decades of intense spectroscopic investigations. Rotational spectroscopy of water vapor has yielded detailed information about the structure and dynamics of isolated water molecules, as well as water dimers and clusters. Nonlinear rotational spectroscopy in the terahertz regime has been developed recently to investigate the rotational dynamics of linear and symmetric-top molecules whose rotational energy levels are regularly spaced. However, it has not been applied to water or other lower-symmetry molecules with irregularly spaced levels. We report the use of recently developed two-dimensional (2D) terahertz rotational spectroscopy to observe high-order rotational coherences and correlations between rotational transitions that were previously unobservable. The results include two-quantum (2Q) peaks at frequencies that are shifted slightly from the sums of distinct rotational transitions on two different molecules. These results directly reveal the presence of previously unseen metastable water complexes with lifetimes of 100 ps or longer. Several such peaks observed at distinct 2Q frequencies indicate that the complexes have multiple preferred bimolecular geometries. Our results demonstrate the sensitivity of rotational correlations measured in 2D terahertz spectroscopy to molecular interactions and complexation in the gas phase.

Atmospheric chemistry of the self-reaction of HO2 radicals: stepwise mechanism versus one-step process in the presence of (H2O)n (n = 1–3) clusters

In the incorporation of the catalyst (H2O)n (n = 1–3) into the HO2 + HO2 → H2O2 + 3O2 reaction, the catalytic effect of water, water dimers and water trimers is mainly derived from the contribution of a single water vapor molecule by a stepwise route.

A comparison between hydrogen and halogen bonding: the hypohalous acid–water dimers, HOX⋯H2O (X = F, Cl, Br)

Hypohalous acids (HOX) are a class of molecules that play a key role in the atmospheric seasonal depletion of ozone and have the ability to form both hydrogen and halogen bonds.

Neutral and anionic phosphate-diesters as molecular templates for the encapsulation of a water dimer

Neutral and anionic phosphate diesters act as molecular templates for the encapsulation of water dimers.

Comment on “Isomerization of the methoxy radical revisited: the impact of water dimers” by B. Bandyopadhyay et al., Phys. Chem. Chem. Phys., 2016, 18, 27728 and “Isomerization of methoxy radical in the troposphere: competition between acidic, neutral and basic catalysts” by P. Kumar, B. Bandyopadhyay et al., Phys. Chem. Chem. Phys., 2017, 19, 278

Isomerization would be unimportant even if it was not slow.

Correction: Comment on “Isomerization of the methoxy radical revisited: the impact of water dimers” by B. Bandyopadhyay et al., Phys. Chem. Chem. Phys., 2016, 18, 27728 and “Isomerization of methoxy radical in the troposphere: competition between acidic, neutral and basic catalysts” by P. Kumar, B. Bandyopadhyay et al., Phys. Chem. Chem. Phys., 2017, 19, 278

Correction for ‘Comment on “Isomerization of the methoxy radical revisited: the impact of water dimers” by B. Bandyopadhyay et al., Phys. Chem. Chem. Phys., 2016, 18, 27728 and “Isomerization of methoxy radical in the troposphere: competition between acidic, neutral and basic catalysts” by P. Kumar, B. Bandyopadhyay et al., Phys. Chem. Chem. Phys., 2017, 19, 278’ by Theodore S. Dibble et al., Phys. Chem. Chem. Phys., 2018, 20, 11481–11482.