Competition between van der Waals and Hydrogen Bonding interactions: Structure of the trans-1-Naphthol/N2 cluster
The excitation energy in the multiphoton ionization spectrum of the trans-1-naphthol/N2 cluster shows only a small red-shift with respect to isolated naphthol, indicating a van-der-Waals ?-bound structure rather than a hydrogen bonded one. In order to confirm this interpretation, high-level electronic structure calculations were performed for several ?- and hydrogen-bonded isomers of this cluster. The calculations were carried out at the second order Moeller Plesset (MP2) level of perturbation theory with the family of correlation consistent basis sets up to quintuple-? quality including corrections for the basis set superposition error and extrapolation to the MP2 complete basis set (CBS) limit. We report the optimal geometries, vibrational frequencies and binding energies (De), also corrected for harmonic zero-point energies (D0), for three energetically low-lying isomers. In all calculations the lowest energy structure was found to be an isomer with the N2 molecule bound to the ?-system of the naphthol ring carrying the OH-group. In the CBS limit its dissociation energy was computed to be D0=2.67 kcal/mol (934 cm-1) as compared to D0=1.28 kcal/mol (448 cm-1) for the H-bound structure. The electronic structure calculations therefore confirm the assignment of the experimental electronic spectrum corresponding to a van-der-Waals ?-bound structure. The energetic stabilization of the ?-bound isomer with respect to the hydrogen bonded one is rather unexpected when compared with previous findings in related systems, in particular phenol/N2.
- Research Organization:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- AC05-76RL01830
- OSTI ID:
- 876935
- Report Number(s):
- PNNL-SA-45664; JPCAFH; KC0301020; TRN: US200608%%95
- Journal Information:
- Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory, Vol. 109, Issue 42; ISSN 1089-5639
- Country of Publication:
- United States
- Language:
- English
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