Intermolecular dissociation energies of dispersively bound complexes of aromatics with noble gases and nitrogen

Sinha, Rajeev K (2018) Intermolecular dissociation energies of dispersively bound complexes of aromatics with noble gases and nitrogen. The Journal Of Chemical Physics, 148 (13). pp. 134302-1. ISSN 0021-9606

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Abstract

We measured accurate intermolecular dissociation energiesD0 of the supersonic jet-cooled complexes of 1-naphthol (1NpOH) with the noble gases Ne, Ar, Kr, and Xe and with N2, using the stimulatedemission pumping resonant two-photon ionization method. The ground-state values D0(S0) for the 1NpOH�S complexes with S= Ar, Kr, Xe, and N2 were bracketed to be within �3.5%; they are 5.67 � 0.05 kJ/mol for S = Ar, 7.34 � 0.07 kJ/mol for S = Kr, 10.8 � 0.28 kJ/mol for S = Xe, 6.67 � 0.08 kJ/mol for isomer 1 of the 1NpOH�N2 complex, and 6.62 � 0.22 kJ/mol for the corresponding isomer 2. For S = Ne, the upper limit is D0 < 3.36 kJ/mol. The dissociation energies increase by 1%-5% upon S0!S1 excitation of the complexes. Three dispersion-corrected density functional theory (DFT-D) methods (B97-D3, B3LYP-D3, and !B97X-D) predict that the most stable form of these complexes involves dispersive binding to the naphthalene “face.” A more weakly bound edge isomer is predicted in which the S moiety is H-bonded to the OH group of 1NpOH; however, no edge isomers were observed experimentally. The B97-D3 calculated dissociation energies D0(S0) of the face complexes with Ar, Kr, and N2 agree with the experimental values within <5%, but the D0(S0) for Xe is 12% too low. The B3LYP-D3 and !B97X-D calculated D0(S0) values exhibit larger deviations to both larger and smaller dissociation energies. For comparison to 1-naphthol, we calculated the D0(S0) of the carbazole complexes with S = Ne, Ar, Kr, Xe, and N2 using the same DFT-D methods. The respective experimental values have been previously determined to be within <2%. Again, the B97- D3 results are in the best overall agreement with experiment.

Item Type: Article
Subjects: Departments at MU > Atomic Molecular Physics
Depositing User: KMC Library
Date Deposited: 17 May 2018 09:39
Last Modified: 17 May 2018 09:39
URI: http://eprints.manipal.edu/id/eprint/150981

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