VO$_2$ under hydrostatic pressure: Isostructural phase transition close to a critical end-point
The high-pressure behavior of monoclinic VO$_2$ is revisited by a combination of Raman spectroscopy and X-ray diffraction on a single crystal under hydrostatic conditions at room temperature. A soft mode is observed up to P$_c$ = 13.9(1) GPa. At this pressure, an isostructural phase transition between two monoclinic phases M$_1$ and M$_1$' hinders this instability. The features of this transformation (no apparent volume jump) indicate that the compression at ambient temperature passes close to a critical point. An analysis based on the Landau theory of phase transitions gives a complete description of the P-T phase diagram. The M1' is characterized by spontaneous displacements of the oxygen sub-lattice without any strong modification of the VV dimers distances nor the twist angle of vanadium chains. The spontaneous displacements of oxygen and the spontaneous deformations of the ($b_{M1}$, $c_{M1}$) plane follow the same quadratic dependence with pressure and scales with spontaneous shifts of the Raman phonons located at 225, 260 and 310 cm$^{-1}$. Pressure-induced shifts of the Raman peaks allows for new assignment of several Raman modes. In particular, the A$_g$(1)+B$_g$(1) modes at 145 cm$^{-1}$ are identified as the vanadium displacive phonons. A second transformation in the metallic phase X, which is found triclinic (P$\bar1$) is observed starting at 32 GPa, with a wide coexistence region (up to 42 GPa). Upon decompression, phase X transforms, between 20 GPa and 3 GPa, to another phase that is neither the M$_1$' nor M$_1$ phase. The structural transitions identified under pressure match with all the previously reported electronic modifications confirming that lattice and electronic degrees of freedom are closely coupled in this correlated material.