Transition from Water Wires to Bifurcated H-Bond Networks in 2-Pyridone·(H2O)n, n = 1–4 Clusters

Mass-selective two-color resonant two-photon ionization (2C-R2PI), UV/UV hole-burning, and infrared (IR) depletion spectra of supersonic jet-cooled 2-pyridone·(H 2 O) n clusters with n = 1-4 have been measured to investigate the local hydration patterns around 2-pyridone (2PY) as a function of cluster size. As shown by others, the IR frequencies of the OH and NH stretches of the n = 1, 2 clusters are characteristic of water wires stretching from the NH to the C═O group of 2PY. We identify two isomers (3A and 3B) of the n = 3 cluster in the 2C-R2PI spectrum and separate them by IR/UV and UV/UV hole-burning techniques. Isomer 3A exhibits a three-membered water wire, extending the n = 1, 2 structural motif. Isomer 3B exhibits bifurcated water wires with the first H 2 O donating to two waters that form H-bonds to the C═O group. This increases the H-bond strength between the NH group of 2PY and the proximal H 2 O molecule, lowering the NH stretch to ∼2800 cm -1 . The n = 4 cluster is also bifurcated with two water wires between the bifurcating H 2 O and the C═O group. The cluster-selective IR spectra are complemented with density-functional calculations using the PW91, B3LYP, B97-D, and M06-2X functionals, where the latter two include long-range dispersive interactions, and with the ab initio correlated SCS-CC2 method. The calculated IR spectra provide firm assignments of the structures of the n = 1-4 cluster structures and allow us to understand the evolution of individual H-bond strengths with increasing cluster size.