Ab initio studies of the water dimer using large basis sets: The structure and thermodynamic energies

Ab initio calculations with various large basis sets have been performed on the water dimer in order to study the structure, energetics, spectra, and electrical properties. As a reference system, the calculations of the water monomer were also performed. The second order Mo/ller‐Plesset perturbation theory (MP2) using a large basis set (O:13s,8p,4d,2f/H:8s,4p,2d) well reproduces various water monomer experimental data except for the somewhat underestimated absolute energy and hyperpolarizability. The monomer energy calculated with the fourth‐order Mo/ller–Plesset perturbation theory (MP4) with the above basis set is −76.407 hartrees, which is only 0.073 hartree above the experimental energy. To compare the theoretical and experimental dimer structures and thermal energies accurately, we summarized the quantum statistical thermodynamic quantities with corrections for anharmonic vibration, rotation, rotation–vibration coupling, and internal rotation. With the correction for the anharmonic binding potential ...

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