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Abstract Continuum polarization over the UV-to-microwave range is due to dichroic extinction (or emission) by asymmetric, aligned dust grains. Scattering can also be an important source of polarization, especially at short wavelengths. Because of both grain alignment and scattering physics, the wavelength dependence of the polarization, generally, traces the size of the aligned grains. Similarly because of the differing wavelength dependencies of dichroic extinction and scattering polarization, the two can generally be reliably separated. Ultraviolet (UV) polarimetry therefore provides a unique probe of the smallest dust grains (diameter$$< 0.09~\upmu \text{m}$$ $<0.09\text{μm}$), their mineralogy and interaction with the environment. However, the current observational status of interstellar UV polarization is very poor with less than 30 lines of sight probed. With the modern, quantitative and well-tested, theory of interstellar grain alignment now available, we have the opportunity to advance the understanding of the interstellar medium (ISM) by executing a systematic study of the UV polarization in the ISM of the Milky Way and near-by galaxies. The Polstar mission will provide the sensitivity and observing time needed to carry out such a program (probing hundreds of stars in the Milky Way and dozens of stars in the LMC/SMC), addressing questions of dust composition as a function of size and location, radiation- and magnetic-field characteristics as well as unveiling the carrier of the 2175 Å extinction feature. In addition, using high-resolution UV line spectroscopy Polstar will search for and probe the alignment of, and polarization from, aligned atoms and ions - so called “Ground State Alignment”, a potentially powerful new probe of magnetic fields in the diffuse ISM. 

UV spectroscopy and spectropolarimetry hold the key to understanding certain aspects of massive stars that are largely inaccessible (or exceptionally difficult) with optical or longer wavelength observations. As we demonstrate, this is especially true for the rapidly-rotating Be and Bn stars, owing to their high temperatures, geometric asymmetries, binary properties, evolutionary history, as well as mass ejection and disks (in the case of Be stars). UV spectropolarimetric observations are extremely sensitive to the photospheric consequences of rapid rotation (i.e. oblateness, temperature, and surface gravity gradients), far beyond the reach of optical wavelengths. Our polarized radiative-transfer modelling predicts that with low-resolution UV spectropolarimetry covering 120-300 nm, and with a reasonable SNR, the inclination angle of a rapid rotator can be determined to within 5 degrees, and the rotation rate to within 1%. The origin of rapid rotation in Be/n stars can be explained by either single-star or binary evolution, but their relative importance is largely unknown. Some Be stars have hot sub-luminous (sdO) companions, which at an earlier phase transferred their envelope (and with it mass and angular momentum) to the present-day rapid rotator. Although sdO stars are small and relatively faint, their flux peaks in the UV making this the optimal observational wavelength regime. Through spectral modelling of a wide range of simulated Be/n+sdO configurations, we demonstrate that high-resolution high-signal-to-noise ratio UV spectroscopy can detect an sdO star even when ∼1,000 times fainter in the UV than its Be/n star companion. This degree of sensitivity is needed to more fully explore the parameter space of Be/n+sdO binaries, which so far has been limited to about a dozen systems with relatively luminous sdO stars. We suggest that a UV spectropolarimetric survey of Be/n stars is the next step forward in understanding this population. Such a dataset would, when combined with population synthesis models, allow for the determination of the relative importance of the possible evolutionary pathways traversed by these stars, which is also crucial for understanding their future evolution and fate.