We report on the optical extinction properties of the clearest ultrapure water measured so far within the wavelength interval between 181 nm and 340 nm (TOC level: 2.6 +/- 0.7 ppb, specific conductivity: 0.055 mu S cm (1)). Our results extend the state-of-the-art extinction spectrum of ultrapure water by 15 nm towards shorter wavelengths and accurately resolve the ultraviolet extinction edge, allowing redefining a straightforward fitting function of the ultraviolet extinction of water (Urbach constant: 0.337 at 25 degrees C). The spectral distribution of our calculated Rayleigh scattering contribution shows a significantly better agreement with the experimental data than those reported in literature. The extinction temperature coefficient was determined in the range from 10 to 30 degrees C as a function of wavelength, showing significantly smaller values than those previously reported and being useful for noninvasively determining the temperature of ultrapure water samples. (C) 2014 Optical Society of America