The recent identification of strongly bound excitons in room temperature anatase TiO 2 single crystals and nanoparticles underscores the importance of bulk many-body effects in samples used for applications. Here, for the first time, we unravel the interplay between many-body interactions and correlations in highly-excited anatase TiO 2 nanoparticles using ultrafast two-dimensional deepultraviolet spectroscopy. With this approach, under non-resonant excitation, we disentangle the optical nonlinearities contributing to the bleach of the lowest direct exciton peak. This allows us to clock the ultrafast timescale of the hot electron thermalization in the conduction band with unprecedented temporal resolution, which we determine to be < 50 fs, due to the strong electronphonon coupling in the material. Our findings call for the design of alternative resonant excitation schemes in photonics and nanotechnology.1 arXiv:1703.07818v2 [cond-mat.mes-hall] 13 Jan 2018In the last decades, anatase TiO 2 has attracted huge interest as one of the most promising materials for a variety of challenging applications, ranging from photocatalysis [1,2] and photovoltaics [3] to sensors [4,5]. Since these technologies involve charge transport, thermalization and localization, they call for studies of the fast electron and hole dynamics, which provide a deep knowledge of the nature of the photogenerated/injected charge carriers and of the energy balance therein. These processes intimately depend on the details of the electronic structure and the presence of many body-effects in the material. Since anatase TiO 2 is a d 0 transition metal oxide, strong electron-electron correlations do not play a substantial role in the electronic structure [6]. Hence, this solid can be classified within the simple band insulator scheme, in which the forbidden energy gap arises as a result of band theory and is not a consequence of the strong on-site Coulomb interaction. However, different to conventional band insulators, anatase TiO 2 represents a peculiar example in which electron-phonon interaction and electron-hole correlation become relatively strong and influence the optical spectra. On the one hand, the presence of a moderately large electron-phonon coupling in anatase TiO 2 has often been invoked to interpret experimental results naturally pointing to the polaronic (self-trapped) picture [7][8][9][10][11][12][13]. Notable examples include the low temperature green photoluminescence (PL) due to self-trapped excitons [14][15][16][17][18][19][20] and the room temperature electron mobilities whose values are limited by strong scattering with phonons [10]. On the other hand, many-body correlations have been thought to be negligible in this material and, as such, they remained widely unexplored. Recently, by employing state-of-the-art experimental [21] and computational techniques [21][22][23][24][25], the substantial role of electron-hole Coulomb correlations was unravelled in the anatase polymorph of TiO 2 . Strongly bound direct excitons were...