Pressure-induced s→d transfer and the equation of state of molybdenum

Abstract

The equations of state of crystalline (bcc) and liquid molybdenum are calculated to pressure-temperature conditions of 600 GPa and 14 000 K with use of the linear muffin-tin orbitals (LMTO) model and corrected rigid-ion sphere (CRIS) model. Our results agree with those of previous work in documenting a pressure-induced shift of electrons from 5s to 4d states, especially above 100 GPa. An analysis of ultrasonic and shock-wave measurements, along with our theoretical findings, documents that the compressibility of bcc Mo becomes enhanced at pressures of 100-200 GPa. The enhanced compression, and possibly an anomalous increase in rigidity, are caused by the pressure-induced s→d transfer. Our study reinforces the use of the Mo equation of state as a calibration standard for ultrahigh-pressure static experiments and, in particular, for the ruby-fluorescence technique.