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Polycrystalline CuMo$_{1-x}$W$_x$O$_4$ solid solutions were studied byresonant X-ray emission spectroscopy (RXES) at the W L$_3$-edge to follow avariation of the tungsten local atomic and electronic structures acrossthermochromic phase transition as a function of sample composition andtemperature. The experimental results were interpreted using ab initiocalculations. The crystal-field splitting parameter for the 5d(W)-states wasobtained from the analysis of the RXES plane and was used to evaluate thecoordination of tungsten atoms. Temperature-dependent RXES measurements weresuccessfully employed to determine the hysteretic behaviour of the structuralphase transition between the $\alpha$ and $\gamma$ phases inCuMo$_{1-x}$W$_x$O$_4$ solid solutions on cooling and heating, even at low($x$<0.10) tungsten content. It was found that tungsten ions have octahedralcoordination for in the whole studied temperature range (90-420 K), whereastheir coordination changes from tetrahedral to octahedral upon cooling forsmaller ($x$ <= 0.15) tungsten content. Nevertheless, some amount of tungstenions was found to co-exists in the octahedral environment at room temperaturefor $x$<0.15. The obtained results correlate well with the color change inthese solid solutions.

Study of the thermochromic phase transition in CuMo$_{1-x}$W$_x$O$_4$ solid solutions at the W L$_3$-edge by resonant X-ray emission spectroscopy