Blue-shifted A-H stretching modes and cooperative hydrogen bonding. 1. Complexes of substituted formaldehyde with cyclic hydrogen fluoride and water clusters

The structures and vibrational spectra of the intermolecular complexes formed by insertion of substituted formaldehyde molecules HRCO (R = H, Li, F, Cl) into cyclic hydrogen fluoride and water clusters are studied at the MP2/aug-cc-pVTZ computational level. Depending on the nature of the substituent R, the cluster type, and its size, the C-H stretching modes of HRCO undergo large blue and partly red shifts, whereas all the F-H and O-H stretching modes of the conventional hydrogen bonds are strongly red-shifted. It is shown that (i) the mechanism of blue shifting can be explained within the concept of the negative intramolecular coupling between C-H and C=O bonds that is inherent to the HRCO monomers, (ii) the blue shifts also occur even if no hydrogen bond is formed, and (iii) variation of the acceptor X or the strength of the C-H...X hydrogen bond may either amplify the blue shift or cause a transition from blue shift to red shift. These findings are illustrated by means of intra- and intermolecular scans of the potential energy surfaces. The performance of the negative intramolecular coupling between C-H and C=O bonds of H(2)CO is interpreted in terms of the NBO analysis of the isolated H(2)CO molecule and H(2)CO interacting with (H2O)n and (HF)n clusters.