Distinguishing steric and electrostatic molecular probe orientational ordering via their effects on reorientation-induced spectral diffusion.

The theoretical framework for reorientation-induced spectral diffusion (RISD) describes the polarization dependence of spectral diffusion dynamics as measured with two-dimensional (2D) correlation spectroscopy and related techniques. Generally, RISD relates to the orientational dynamics of the molecular chromophore relative to local electric fields of the medium. The predictions of RISD have been shown to be very sensitive to both restricted orientational dynamics (generally arising from steric hindrance) and the distribution of local electric fields relative to the probe (electrostatic ordering). Here, a theory that combines the two effects is developed analytically and supported with numerical calculations. The combined effects can smoothly vary the polarization dependence of spectral diffusion from the purely steric case (least polarization dependence) to the purely electrostatic case (greatest polarization dependence). Analytic approximations of the modified RISD equations were also developed using the orientational dynamics of the molecular probe and two order parameters describing the degree of electrostatic ordering. It was found that frequency-dependent orientational dynamics are a possible consequence of the combined electrostatic and steric effects, providing a test for the applicability of this model to experimental systems. The modified RISD equations were then used to successfully describe the anomalous polarization-dependent spectral diffusion seen in 2D infrared spectroscopy in a polystyrene oligomer system that exhibits frequency-dependent orientational dynamics. The degree of polarization-dependent spectral diffusion enables the extent of electrostatic ordering in a chemical system to be quantified and distinguished from steric ordering.