Vibrational Stark fields in carboxylic acid dimers.

Carboxylic acids form exceptionally stable dimers and have been used to model proton and double proton transfer processes. The stabilization energies of the carboxylic acid dimers are very weakly dependent on the nature of substitution. However, the electric field experienced by the OH group of a particular carboxylic acid is dependent more on the nature of the substitution on the dimer partner. In general, the electric field was higher when the partner was substituted with an electron-donating group and lower with an electron-withdrawing substituent on the partner. The Stark tuning rate (Δ) of the O-H stretching vibrations calculated at the MP2/aug-cc-pVDZ level was found to be weakly dependent on the nature of substitution on the carboxylic acid. The average Stark tuning rate of O-H stretching vibrations of a particular carboxylic acid when paired with other acids was 5.7 cm-1 (MV cm-1)-1, while the corresponding average Stark tuning rate of the partner acids due to a particular carboxylic acid was 21.9 cm-1 (MV cm-1)-1. The difference in the Stark tuning rate is attributed to the primary and secondary effects of substitution on the carboxylic acid. The average Stark tuning rate for the anharmonic O-D frequency shifts is about 40-50% higher than the corresponding harmonic O-D frequency shifts calculated at the B3LYP/aug-cc-pVDZ level, much greater than the typical scaling factors used, indicating the strong anharmonicity of O-H/O-D oscillators in carboxylic acid dimers. Finally, the linear correlation observed between pKa and the electric field was used to estimate the pKa of fluoroformic acid to be around 0.9.

Internal electric fields in methanol [MeOH]2-6 clusters.

Water and methanol are well known solvents showing cooperative hydrogen bonding, however the differences in the hydrogen bonding pattern in water and methanol are due to the presence of the methyl group in methanol. The presence of the methyl group leads to formation of C-HO hydrogen bonds apart from the usual O-HO hydrogen bonds. The electric fields evaluated along the hydrogen bonded donor OH and CH groups reveal that the C-HO hydrogen bonds can significantly influence the structure and energetics (by about 20%) of methanol clusters. A linear Stark effect was observed on the hydrogen bonded OH groups in methanol clusters with a Stark tuning rate of 3.1 cm-1 (MV cm-1)-1 as an average behaviour. Furthermore, the Stark tuning of the OH oscillators in methanol depends on their hydrogen bonding environment wherein molecules with the DAA motif show higher rates than the rest. The present work suggests that the OH group of methanol has higher sensitivity as a vibrational probe relative to the OH group of water.

Synthesis and structure of arylselenium(ii) and aryltellurium(ii) cations based on rigid 5-tert-butyl-1,3-bis-(N-pentylbenzimidazol-2'-yl)benzenes.

The transmetalation reactions of a mercury precursor, [Pentyl(N^C^N)HgCl] (19), with selenium halides (SeCl4, SeBr4, and SeCl2) were attempted to obtain the corresponding organoselenium trichloride [Pentyl(N^C^N)SeCl3], tribromide [Pentyl(N^C^N)SeBr3], and monochloride [Pentyl(N^C^N)SeCl], respectively [(N^C^N) = 5-tert-butyl-1,3-bis-(N-pentyl-benzimidazol-2'-yl)phenyl]. However, in all the cases, a very facile ionization of the Se-halogen bond was observed leading to the isolation of a new class of air stable arylselenium(ii) complexes: [Pentyl(N^C^N)Se+]2[HgCl4]2- (20) and [Pentyl(N^C^N)Se+]2[HgBr4]2- (21). This is the first report on the formation of NCN pincer-based arylselenium(ii) cations via the transmetalation route. Similar reactions were further investigated with several tellurium precursors: {TeCl4, TeBr4 and TeI2} which resulted in the formation of analogous aryltellurium(ii) complexes: [Pentyl(N^C^N)Te+]2[HgCl4]2- (22), [Pentyl(N^C^N)Te+][Cl]- (23), [Pentyl(N^C^N)Te+]2[HgBr4]2- (24), [Pentyl(N^C^N)Te+][Br]- (25) and [Pentyl(N^C^N)Te+]4[Hg2Cl4.72I3.28]4- (26). These are only the second set of examples of aryltellurium cations (hypervalent 10-Te-3 species) with the NCN pincer-based ligand, characterised by X-ray crystallographic studies. The crystallographic studies show a strong SeN/TeN intramolecular interaction, which is confirmed by NBO calculations suggesting the donation of a lone pair of electrons on nitrogen to a lone p-vacancy on selenium/tellurium atoms. The analysis based on NPA derived charges indicates that the contribution of SeN interactions to the electrostatic stabilization energy is in the range of 40-60%, whereas TeN interactions have a contribution of about 84% and more, attributed to the differences in the electronegativity of selenium and tellurium. Furthermore, the formation of arylselenium(ii) and aryltellurium(ii) complexes was favoured due to the presence of the σ-hole on the Se/Te centres.

Insights into acid dissociation of HCl and HBr with internal electric fields.

The electric field experienced by an acid molecule in the acid-water cluster depends on its local environment comprising of surrounding water molecules. A critical field of about 193 and 163 MV cm-1 is required for the dissociation of HCl and HBr, respectively, and is associated with the arrangement of water molecules around the acid. The critical field required for dissociation of isolated HCl and HBr is 510 and 462 MV cm-1, respectively. Hence the solvation of the proton and the halide anion by water molecules substantially lowers the critical electric field by about 300 MV cm-1, relative to vacuum.

Internal electric fields in small water clusters [(H2O)n; n = 2-6].

The electric field experienced by a water molecule within a water cluster depends on its position relative to the rest of the water molecules. The stabilization energies and the red-shifts in the donor O-H stretching vibrations in the water clusters increase with the cluster size concomitant with the increase in the electric field experienced by the donor O-H of a particular water molecule due to the hydrogen bonding network. The red-shifts in O-H stretching frequencies show a spread of about ±100 cm(-1) against the corresponding electric fields. Deviations from linearity were marked in the region of 100-160 MV cm(-1), which can be attributed to the strain in the hydrogen bonding network, especially for structures with DDAA and DDA motifs. The linear Stark effect holds up to 200 MV cm(-1) of internal electric field for the average red-shifts in the O-H stretching frequencies, with a Stark tuning rate of 2.4 cm(-1) (MV cm(-1))(-1), suggesting the validity of the classical model in small water clusters.