Chirality-induced signals in coherent multidimensional spectroscopy of excitons.

The nonlocal second- and third-order susceptibilities of an isotropic ensemble of aggregates are calculated by solving the nonlinear exciton equations which map the system into coupled anharmonic oscillators. Both electric and magnetic contributions are included using the minimal-coupling Hamiltonian. The various tensor components are evaluated to first order in the optical wave vector k. Additional structural information about the interchromophore distances, which is not accessible through zeroth-order contributions (the dipole approximation), is contained to the first order in k. New resonant second- and third-order signals predicted for chiral molecules provide multidimensional extensions of circular dichroism spectroscopy. Numerical simulations demonstrate the sensitivity of third-order signals to the secondary structural motiffs of peptides.