Intermolecular dissociation energies of 1-naphthol complexes with large dispersion-energy donors: Decalins and adamantane

Sinha, Rajeev K (2020) Intermolecular dissociation energies of 1-naphthol complexes with large dispersion-energy donors: Decalins and adamantane. The Journal Of Chemical Physics, 152. pp. 1-14. ISSN 0021-9606

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Abstract

The ground-state intermolecular dissociation energies D0(S0) of supersonic-jet cooled intermolecular complexes of 1- aphthol (1NpOH) with the bi- and tricycloalkanes trans-decalin, cis-decalin, and adamantane were measured using the stimulated-emission-pumping/resonant two-photon ionization (SEP-R2PI) method. Using UV/UV holeburning, we identified two isomers (A and B) of the adamantane and trans-decalin complexes and four isomers (A–D) of the cis-decalin complex. For 1NpOH⋅adamantane A and B, the D0(S0) values are 21.6 ± 0.15 kJ/mol and 21.2 ± 0.32 kJ/mol, those of 1NpOH⋅trans-decalin A and B are 28.7 ± 0.3 kJ/mol and 28.1 ± 0.9 kJ/mol, and those of 1NpOH⋅cis-decalin A and B are 28.9 ± 0.15 kJ/mol and 28.7 ± 0.3 kJ/mol. Upon S0 → S1 electronic excitation of the 1NpOH moiety, the dissociation energies of adamantane, trans-decalin, and the cis-decalin isomer C change by <1% and those of cis-decalin isomers A, B, and D increase only slightly (1%–3%). This implies that the hydrocarbons are dispersively adsorbed to a naphthalene “face.” Calculations using the dispersion-corrected density functional theory methods B97-D3 and B3LYP-D3 indeed predict that the stable structures have face geometries.The B97-D3 calculated D0(S0) values are within 1 kJ/mol of the experiment, while B3LYP-D3 predicts D0 values that are 1.4–3.3 kJ/mol larger.Although adamantane has been recommended as a “dispersion-energy donor,” the binding energies of the trans- and cis-decalin adducts to 1NpOH are 30% larger than that of adamantane. In fact, the D0 value of 1NpOH⋅adamantane is close to that of 1NpOH⋅cyclohexane, reflecting the nearly identical contact layer between the two molecules

Item Type: Article
Subjects: Departments at MU > Atomic Molecular Physics
Depositing User: KMC Library
Date Deposited: 01 Jul 2020 08:44
Last Modified: 01 Jul 2020 08:44
URI: http://eprints.manipal.edu/id/eprint/155163

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