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Extra info for Problem - Reaction - Solution
2a illustrates the geometry of the monomer and the directions of the three principal moments of inertia; the dimer is depicted in Fig. 2b. 2 reports the total mass of each species in the first row, followed by the translational energy at 25° C, 3/2 RT. 3. The moments of inertia are strongly affected by dimerization. The greater distances of the atoms from the center of mass of the dimer, as compared to the smaller monomer, account for the much increased values of Ib and Ic. 9). Hence, Erot amounts to —3/2 RT as was true for Etrans.
In the gas phase, which most quantum calculations mimic, the H-bond energy is typically in the range of 2 to 15 kcal/mol. This interaction is weaker than most covalent bonds by about one order of magnitude, but stronger than nondirectional "noncovalent" forces which tend to be less than 2 kcal/mol. Nonetheless, this range is meant only as a general rule of thumb rather than as a strict threshold. One should not consider the range as exclusively the province of H-bonds, nor should interactions be discounted as H-bonds merely for lying outside this range.
For example, early on, Karlstrom and Sadlej170 argued that these effects can be beneficial in that the properties of each monomer are improved by the enlargement of the basis set, as would occur if the additional functions were centered on the molecule itself rather than its partner. However, later work indicated that secondary BSSE typically represents another artifact that deteriorates the quality of the calculation. Latajka and Scheiner17S took as a model the interaction between a Li ' cation and a neutral molecule of water and showed that Quantum Chemical Framework 25 the secondary BSSE can be quite large, comparable in magnitude to the primary effect.