Excitonic splittings in jet-cooled molecular dimers

In more than 60 years of research on molecular excitons, there has been extensive theoretical work but few experimental investigations have rigorously tested the predictions of exciton coupling theories. In centrosymmetric doubly H-bonded molecular dimers with identical chromophores, the S0-->S1 electronic transition dipole moments of the monomers combine in a parallel and antiparallel fashion, giving the S0-S1 and S0-->S2 transitions of the dimer. One of these is strictly symmetry-forbidden and the other fully allowed. Minimal perturbations such as 12C/13C or H/D isotopic substitution lift the symmetry restrictions sufficiently to render both transitions allowed. The excitonic (Davydov) splitting can then be measured as the energy difference between the respective vibrationless O0(0) bands. We have measured the mass-specific vibronic spectra of the centrosymmetric H-bonded dimers (2-pyridone)2 and (2-aminopyridine)2 that are supersonically cooled to a few K and isolated in molecular beams, using two-color resonant two-photon ionization spectroscopy. Comparison of the all-12C- and 13C- isotopomer spectra yield excitonic splittings of delta(exp) = 43.5 and 10.5 cm(-1), respectively. The corresponding splittings calculated by high-level ab initio methods (RI-CC2/aug-cc-pVTZ) are 20 to 50 times larger. These purely electronic ab initio exciton splittings need to be reduced ('quenched') by vibronic coupling to the optically active vibrational modes. Only after quenching are the experimentally observed exciton splittings correctly reproduced.