Super-Resolved 3D Mapping of Molecular Orientation Using Vibrational Techniques
Paulina Kozioł, Karolina Kosowska, Danuta Liberda, Ferenc Borondics, Tomasz P. Wróbel
Abstract
When a sample has an anisotropic structure, it is possible to obtain additional information controlling the polarization of incident light. With their straightforward instrumentation approaches, infrared (IR) and Raman spectroscopies are widely popular in this area. Single-band-based determination of molecular in-plane orientation, typically used in materials science, is here extended by the concurrent use of two vibration bands, revealing the orientational ordering in three dimension. The concurrent analysis was applied to IR spectromicroscopic data to obtain orientation angles of a model polycaprolactone spherulite sample. The applicability of this method spans from high-resolution, diffraction-limited Fourier transform infrared (FT-IR) and Raman imaging to super-resolved optical photothermal infrared (O-PTIR) imaging. Due to the nontomographic experimental approach, no image distortion is visible and nanometer scale orientation domains can be observed. Three-dimensional (3D) bond orientation maps enable in-depth characterization and consequently precise control of the sample's physicochemical properties and functions.