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Oldani AN, Ferrero JC, Pino GA: Effect of the intermolecular hydrogen bond conformation on the structure and reactivity of the p-cresol (H2O)(NH3) van der Waals complex. Phys Chem Chem Phys. 2009 Nov 28;11(44):10409-16. Epub 2009 Sep 25.
The structure and reactivity of p-CrOH (NH (3))(2) and p-CrOH (H (2) O)(NH (3)) complexes were studied using mass-resolved one-colour resonance-enhanced multi-photon ionization and laser-induced fluorescence (LIF) spectroscopy together with DFT calculations. At the excitation energy of this work, the S (1) state of p-CrOH (NH (3))(2) shows a sub-nanosecond lifetime, as determined by time-resolved LIF spectra, as a consequence of a hydrogen transfer process that results in NH (4)(NH (3)) as a reaction product. Substitution of NH (3) by H (2) O closes the reaction channel as evidenced by the absence of excited-state hydrogen transfer (ESHT) reaction products, (H (3) O (NH (3)) or NH (4)(H (2) O)) and results in a dramatic effect on the S (1) lifetime of the p-CrOH (H (2) O)(NH (3)) complex which rises to (12 +/- 2) ns. According to density functional theory calculations, the most stable isomer of the p-CrOH (H (2) O)(NH (3)) complex is a cyclic structure, in which H (2) O acts as the H acceptor of the phenolic OH group (c-OH-H (2) O-NH (3)). However, the ESHT process is energetically disallowed upon electronic excitation. |
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