Two-State or Non-Two-State? An Excess Spectroscopy-based Approach to Differentiate the Existing Forms of Molecules in Liquids Mixtures

Characterization/identification of the clusters/associates in liquids has long been a challenging topic. In this paper, we report a method to identify molecules with two different existing forms in a binary liquid solution. In this so-called two-state situation, the excess infrared spectra of a vibration mode of the respective molecule will show identical band shape if the other component is transparent in the region. More conveniently, the positions of the positive peak, negative peak, and zero-value will be seen to be fixed with varying compositions of the binary system. In the case of non-two-state mixtures, for example the mere solvation of solute by solvent, those positions will be variable. The conclusions are supported/demonstrated by computational simulation and experiments on two binary systems, D(2)O−H(2)O and C(6)F(5)I−cyclo-C(6)H(12).