Wetting Camphor: Multi-Isotopic Substitution Identifies the Complementary Roles 
of Hydrogen Bonding and Dispersive Forces

Pérez, Cristóbal; Krin, Anna; Steber, Amanda L.; López, Juan C.; Kisiel, Zbigniew; Schnell, Melanie

doi:10.1021/acs.jpclett.5b02541

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Wetting Camphor: Multi-Isotopic Substitution Identifies the Complementary Roles of Hydrogen Bonding and Dispersive Forces

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Pérez, Cristóbal
Structure and Dynamics of Cold and Controlled Molecules, Independent Research Groups, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society;
Center for Free-Electron Laser Science, D-22761 Hamburg, Germany;

/persons/resource/persons146333

Krin, Anna
Structure and Dynamics of Cold and Controlled Molecules, Independent Research Groups, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society;
Center for Free-Electron Laser Science, D-22761 Hamburg, Germany;

/persons/resource/persons188134

Steber, Amanda L.
Structure and Dynamics of Cold and Controlled Molecules, Independent Research Groups, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society;
Center for Free-Electron Laser Science, D-22761 Hamburg, Germany;
The Hamburg Centre for Ultrafast Imaging at the University of Hamburg, D-22761 Hamburg, Germany;

López, Juan C.
Structure and Dynamics of Cold and Controlled Molecules, Independent Research Groups, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society;
Departamento de Quimica Fisica y Quimica Inorganica, Facultad de Ciencias, Universidad de Valladolid, 47011 Valladolid, Spain;

/persons/resource/persons22077

Schnell, Melanie
Structure and Dynamics of Cold and Controlled Molecules, Independent Research Groups, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society;
Center for Free-Electron Laser Science, D-22761 Hamburg, Germany;
The Hamburg Centre for Ultrafast Imaging at the University of Hamburg, D-22761 Hamburg, Germany;

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http://dx.doi.org/10.1021/acs.jpclett.5b02541
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Citation

Pérez, C., Krin, A., Steber, A. L., López, J. C., Kisiel, Z., & Schnell, M. (2016). Wetting Camphor: Multi-Isotopic Substitution Identifies the Complementary Roles of Hydrogen Bonding and Dispersive Forces. The Journal of Physical Chemistry Letters, 7(1), 154-160. doi:10.1021/acs.jpclett.5b02541.

Cite as: https://hdl.handle.net/11858/00-001M-0000-0029-4DC2-0

Abstract

Using broadband rotational spectroscopy, we report here on the delicate interplay between hydrogen bonds and dispersive forces when an unprecedentedly large organic molecule (camphor, C10H16O) is microsolvated with up to three molecules of water. Unambiguous assignment was achieved by performing multi H218O isotopic substitution of clustered water molecules. The observation of all possible mono- and multi-H218O insertions in the cluster structure yielded accurate structural information that is not otherwise achievable with single-substitution experiments. The observed clusters exhibit water chains starting with a strong hydrogen bond to the C═O group and terminated by a mainly van der Waals (dispersive) contact to one of the available sites at the monomer moiety. The effect of hydrogen bond cooperativity is noticeable, and the O···O distances between the clustered water subunits decrease with the number of attached water molecules. The results reported here will further contribute to reveal the hydrophobic and hydrophilic interactions in systems of increasing size.