Abstract: | The Raman spectroscopic characterization of the orthorhombic phase of Cs2RuO4 was carried out by means of group theory and quantum chemical analysis. Multiple models based on ruthenate (VI+) tetrahedra were tested, and characterization of all the active Raman modes was achieved. A comparison of Raman spectra of Cs2RuO4, Cs2MoO4, and Cs2WO4 was also performed. Raman laser heating induced a phase transition from an ordered to a disordered structure. The temperature‐phase transition was calculated from the anti‐Stokes/Stokes ratio and compared with the ones measured at macroscopic scale. The phase transition is connected with tilting and/or rotations of RuO4 tetrahedra, which lead to a disorder at the RuO4 sites. © 2015 The Authors. Journal of Raman Spectroscopy published by John Wiley & Sons Ltd. |