Theoretical investigations into the blue-shifting hydrogen bond in benzene complexes

The benzene(...)X complexes (X=benzene, antracene, ovalene) were optimised at the MP2/6-31G** level with the C-2v symmetry of the complex and planarity of the proton acceptor being preserved. The resulting stabilisation energies amount to 1.2, 2.3 and 2.9 kcal mol(-1), and the C-H bond of the proton donor is contracted by 0.0035, 0.0052 and 0.0055 A, respectively. The contraction is connected with a blue-shift of the C-H stretch vibration frequency. A two-dimensional anharmonic vibration treatment based on a MP2/6-31G** potential energy surface yields the following blue shifts for the complexes studied: 28, 42 and 43 cm(-1) . The dominant attraction in the complexes is London dispersion, while the attractive contribution from electrostatic quadrupole-quadrupole interactions is considerably smaller.