We performed density functional theory (DFT) calculations using the WB97Xd functional with a dispersion correction term and the 6-31G(d,p) basis set to study the contributions of pi-pi stacking and hydrogen-bonding interactions to the aggregation of asphaltene model compounds containing a 2,2'-bipyridine moiety covalently bonded to one (monosubstituted) and two (disubstituted) aromatic hydrocarbon moieties (phenyl, naphthyl, anthracyl, phenanthryl, and pyrenyl) through ethylene tethers. In these compounds, the N atoms of the 2,2'-bipyridine moiety provide lone pairs for hydrogen bonding to water molecules present in solution. The aggregation strength of the homodimers of these model compounds is evaluated in terms of the aggregation energies, enthalpies, and Delta G(298), as well as the pi-pi interaction distances. Geometry optimization and thermochemistry analysis results show that the homodimers of both mono- and disubstituted compounds are stable and have a negative Delta G(298) of aggregation because of pi-pi stacking interactions. Two water bridges containing one, two, or three water molecules per bridge span between two monomers and provide additional stabilization of the homodimers because of hydrogen bonding. The stabilization of the monosubstituted homodimers is the largest with two water molecules per bridge, whereas the stabilization of the disubstituted homodimers is the largest with three water molecules per bridge. The calculated H-1 nuclear magnetic resonance chemical shifts for the monomers and dimers of the three model compounds of this series synthesized to date are in excellent agreement with experimental results for dilute and concentrated solutions in chloroform, respectively (Tan, X.; Fenniri, H.; Gray, M. R. Water enhances the aggregation of model asphaltenes in solution via hydrogen bonding. Energy Fuels 2009, 23, 3687). The Delta H and Delta G(298) results show that hydrogen bonding is as important as pi-pi interactions for asphaltene aggregation.