NH...pi hydrogen bonds occur frequently between the amino acid side groups in proteins and peptides. Data-mining studies of protein crystals find that similar to 80% of the T-shaped histidine...aromatic contacts are CH...pi, and only similar to 20% are NH...pi interactions. We investigated the infrared (IR) and ultraviolet (UV) spectra of the supersonic-jet-cooled imidazole.benzene (Im.Bz) complex as a model for the NH...pi interaction between histidine and phenylalanine. Ground- and excited-state dispersion-corrected density functional calculations and correlated methods (SCS-MP2 and SCS-CC2) predict that Im.Bz has a C-s-symmetric T-shaped minimum-energy structure with an NH...pi hydrogen bond to the Bz ring; the NH bond is tilted 12 degrees away from the Bz C-6 axis. IR depletion spectra support the T-shaped geometry: The NH stretch vibrational fundamental is red shifted by -73 cm(-1) relative to that of bare imidazole at 3518 cm(-1), indicating a moderately strong NH...pi interaction. While the S-0(A(1g)) -> S-1(B-2u) origin of benzene at 38 086 cm(-1) is forbidden in the gas phase, Im.Bz exhibits a moderately intense S-0 -> S-1 origin, which appears via the D-6h -> C-s symmetry lowering of Bz by its interaction with imidazole. The NH...pi ground-state hydrogen bond is strong, D-e=22.7 kJ/mol (1899 cm(-1)). The combination of gas-phase UV and IR spectra confirms the theoretical predictions that the optimum Im.Bz geometry is T shaped and NH...pi hydrogen bonded. We find no experimental evidence for a CH...pi hydrogen-bonded ground-state isomer of Im.Bz. The optimum NH...pi geometry of the Im.Bz complex is very different from the majority of the histidine.aromatic contact geometries found in protein database analyses, implying that the CH...pi contacts observed in these searches do not arise from favorable binding interactions but merely from protein side-chain folding and crystal-packing constraints. The UV and IR spectra of the imidazole.(benzene)(2) cluster are observed via fragmentation into the Im.Bz(+) mass channel. The spectra of Im.Bz and Im.Bz(2) are cleanly separable by IR hole burning. The UV spectrum of Im.Bz(2) exhibits two 000 bands corresponding to the S-0 -> S-1 excitations of the two inequivalent benzenes, which are symmetrically shifted by -86/+88 cm(-1) relative to the 0(0)(0) band of benzene.