Intermolecular dissociation energies D0(S0) of the supersonic jet-cooled complexes of 1-naphthol (1NpOH) with cyclopentane, cyclohexane, and cycloheptane were determined to within % using the stimulated-emission pumping resonant two-photon ionization method. The ground state D0(S0) values are bracketed as kJ/mol for 1NpOH⋅cyclopentane, kJ/mol for 1NpOH⋅cyclohexane, and kJ/mol for two isomers of 1NpOH⋅cycloheptane. Upon excitation of the 1-naphthol chromophore, the dissociation energies of the 1NpOH⋅cycloalkane complexes increase from 0.1% to 3%. Three dispersion-corrected density functional theory (DFT) methods predict that the cycloalkane moieties are dispersively bound to the naphthol face via London-type interactions, similar to the “face” isomer of the 1-naphthol⋅cyclopropane complex [S. Maity et al., J. Chem. Phys. 145, 164304 (2016)]. The experimental and calculated D0(S0) values of the cyclohexane and cyclopentane complexes are practically identical, although the polarizability of cyclohexane is % larger than that of cyclopentane. Investigation of the calculated pairwise atomic contributions to the D2 dispersion energy reveals that this is due to subtle details of the binding geometries of the cycloalkanes relative to the 1-naphthol ring. The B97-D3 DFT method predicts dissociation energies within about % of experiment, including the cyclopropane face complex. The B3LYP-D3 and ωB97X-D calculated dissociation energies are 7–9 and 13–20% higher than the experimental D0(S0) values. Without dispersion correction, all the complexes are calculated to be unbound.
Skip Nav Destination
Article navigation
28 December 2016
Research Article|
December 29 2016
Intermolecular dissociation energies of dispersively bound 1-naphthol⋅cycloalkane complexes
Surajit Maity;
Surajit Maity
a)
Departement für Chemie und Biochemie,
Universität Bern, Freiestrasse 3
, CH-3000 Bern, Switzerland
Search for other works by this author on:
Philipp Ottiger;
Philipp Ottiger
Departement für Chemie und Biochemie,
Universität Bern, Freiestrasse 3
, CH-3000 Bern, Switzerland
Search for other works by this author on:
Franziska A. Balmer;
Franziska A. Balmer
Departement für Chemie und Biochemie,
Universität Bern, Freiestrasse 3
, CH-3000 Bern, Switzerland
Search for other works by this author on:
Richard Knochenmuss;
Richard Knochenmuss
Departement für Chemie und Biochemie,
Universität Bern, Freiestrasse 3
, CH-3000 Bern, Switzerland
Search for other works by this author on:
Samuel Leutwyler
Samuel Leutwyler
b)
Departement für Chemie und Biochemie,
Universität Bern, Freiestrasse 3
, CH-3000 Bern, Switzerland
Search for other works by this author on:
a)
Current address: Department of Chemistry, IIT Hyderabad, Kandi, Sangareddy-502285, Telangana, India
J. Chem. Phys. 145, 244314 (2016)
Article history
Received:
October 21 2016
Accepted:
December 13 2016
Citation
Surajit Maity, Philipp Ottiger, Franziska A. Balmer, Richard Knochenmuss, Samuel Leutwyler; Intermolecular dissociation energies of dispersively bound 1-naphthol⋅cycloalkane complexes. J. Chem. Phys. 28 December 2016; 145 (24): 244314. https://doi.org/10.1063/1.4973013
Download citation file:
Sign in
Don't already have an account? Register
Sign In
You could not be signed in. Please check your credentials and make sure you have an active account and try again.
Sign in via your Institution
Sign in via your InstitutionPay-Per-View Access
$40.00
Citing articles via
Related Content
Auger electron spectra of the cycloalkanes C3 through C6
J. Chem. Phys. (January 1981)
Consistent Force Field for Calculations of Conformations, Vibrational Spectra, and Enthalpies of Cycloalkane and n‐Alkane Molecules
J. Chem. Phys. (September 2003)
Intermolecular dissociation energies of 1-naphthol complexes with large dispersion-energy donors: Decalins and adamantane
J. Chem. Phys. (March 2020)
Symmetry and Conformation of the Cycloalkanes
J. Chem. Phys. (December 2003)
Neuromimetic approach to 13C NMR shifts prediction for methyl substituted cycloalkanes
AIP Conference Proceedings (April 1995)