Hydrogen Bonding in the Dimer and Monohydrate of 2-Adamantanol: A Test Case for Dispersion-Corrected Density Functional Methods
Marcos Juanes,
Rizalina Tama Saragi,
Cristóbal Pérez,
Luca Evangelisti,
Lourdes Enríquez,
Martín Jaraíz,
Alberto Lesarri
Affiliations
Marcos Juanes
Departamento de Química Física y Química Inorgánica, Facultad de Ciencias—I.U. CINQUIMA, Universidad de Valladolid, Paseo de Belén, 7, 47011 Valladolid, Spain
Rizalina Tama Saragi
Departamento de Química Física y Química Inorgánica, Facultad de Ciencias—I.U. CINQUIMA, Universidad de Valladolid, Paseo de Belén, 7, 47011 Valladolid, Spain
Cristóbal Pérez
Departamento de Química Física y Química Inorgánica, Facultad de Ciencias—I.U. CINQUIMA, Universidad de Valladolid, Paseo de Belén, 7, 47011 Valladolid, Spain
Luca Evangelisti
Dipartimento di Chimica ‘‘Giacomo Ciamician’’, Università di Bologna, Via Selmi, 2, 40126 Bologna, Italy
Lourdes Enríquez
Departamento de Electrónica, Escuela Técnica Superior de Ingenieros de Telecomunicación, Universidad de Valladolid, Paseo de Belén, 15, 47011 Valladolid, Spain
Martín Jaraíz
Departamento de Electrónica, Escuela Técnica Superior de Ingenieros de Telecomunicación, Universidad de Valladolid, Paseo de Belén, 15, 47011 Valladolid, Spain
Alberto Lesarri
Departamento de Química Física y Química Inorgánica, Facultad de Ciencias—I.U. CINQUIMA, Universidad de Valladolid, Paseo de Belén, 7, 47011 Valladolid, Spain
Weakly-bound intermolecular clusters constitute reductionist physical models for non-covalent interactions. Here we report the observation of the monomer, the dimer and the monohydrate of 2-adamantanol, a secondary alcohol with a bulky ten-carbon aliphatic skeleton. The molecular species were generated in a supersonic jet expansion and characterized using broadband chirped-pulse microwave spectroscopy in the 2–8 GHz frequency region. Two different gauche-gauche O-H···O hydrogen-bonded isomers were observed for the dimer of 2-adamantanol, while a single isomer was observed for the monomer and the monohydrate. The experimental rotational parameters were compared with molecular orbital calculations using density functional theory (B3LYP-D3(BJ), B2PLYP-D3(BJ), CAM-B3LYP-D3(BJ), ωB97XD), additionally providing energetic and electron density characterization. The shallow potential energy surface makes the dimer an interesting case study to benchmark dispersion-corrected computational methods and conformational search procedures.
