Imaging 3D molecular orientation by orthogonal-pair polarization IR microscopy.

Anisotropic molecular alignment occurs ubiquitously and often heterogeneously in three dimensions (3D). However, conventional imaging approaches based on polarization can map only molecular orientation projected onto the 2D polarization plane. Here, an algorithm converts conventional polarization-controlled infrared (IR) hyperspectral data into images of the 3D angles of molecular orientations. The polarization-analysis algorithm processes a pair of orthogonal IR transition-dipole modes concurrently; in contrast, conventional approaches consider individual IR modes separately. The orthogonal-pair polarization IR (OPPIR) method, introduced theoretically but never demonstrated experimentally, was used to map the 3D orientation angles and the order parameter of the local orientational distribution of polymer chains in a poly(ε-caprolactone) film. The OPPIR results show that polymer chains in the semicrystalline film are aligned azimuthally perpendicular to the radial direction of a spherulite and axially tilted from the film normal direction. This newly available information on the local alignments in continuously distributed molecules helps to understand the molecular-level structure of highly anisotropic and spatially heterogeneous materials.