van der Waals Dispersion Potential between Excited Chiral Molecules via the Coupling of Induced Dipoles

Abstract

The retarded van der Waals dispersion potential between two excited chiral molecules was calculated using an approach, in which electric and magnetic dipole moments are induced in each particle by fluctuations in the vacuum electromagnetic field. An expectation value of the coupling of the moments at different centres to the dipolar interaction tensors was taken over excited matter states and the ground state radiation field, the former yielding excited molecular polarisabilities and susceptibilities, and the latter field–field spatial correlation functions. The dispersion potential term proportional to the mixed dipolar polarisability is discriminatory, dependent upon molecular handedness, and contains additional terms due to transitions that de-excite each species as well as the usual u-integral term over imaginary frequency, which applies to both upward and downward transitions. Excited state dispersion potentials of a comparable order of magnitude involving paramagnetic and diamagnetic couplings were also computed. Pros and cons of the method adopted are compared to other commonly used approaches.