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Intermolecular dissociation energies of 1-naphthol complexes with large dispersion-energy donors: Decalins and adamantane.
- Source :
- Journal of Chemical Physics; 3/14/2020, Vol. 152 Issue 10, p1-14, 14p, 1 Color Photograph, 4 Charts, 10 Graphs
- Publication Year :
- 2020
-
Abstract
- The ground-state intermolecular dissociation energies D<subscript>0</subscript>(S<subscript>0</subscript>) of supersonic-jet cooled intermolecular complexes of 1-naphthol (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 D<subscript>0</subscript>(S<subscript>0</subscript>) 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 S<subscript>0</subscript> → S<subscript>1</subscript> 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 D<subscript>0</subscript>(S<subscript>0</subscript>) values are within 1 kJ/mol of the experiment, while B3LYP-D3 predicts D<subscript>0</subscript> 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 D<subscript>0</subscript> value of 1NpOH·adamantane is close to that of 1NpOH·cyclohexane, reflecting the nearly identical contact layer between the two molecules. [ABSTRACT FROM AUTHOR]
Details
- Language :
- English
- ISSN :
- 00219606
- Volume :
- 152
- Issue :
- 10
- Database :
- Complementary Index
- Journal :
- Journal of Chemical Physics
- Publication Type :
- Academic Journal
- Accession number :
- 142252253
- Full Text :
- https://doi.org/10.1063/1.5144773