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Pressure-induced structural change in liquid GeI<sub>4</sub>.

The similarity in the shape of the melting curve of GeI&lt;sub&gt;4&lt;/sub&gt; to that of SnI&lt;sub&gt;4&lt;/sub&gt; suggests that a liquid-liquid transition as observed in liquid SnI&lt;sub&gt;4&lt;/sub&gt; is also expected to occur in liquid GeI&lt;sub&gt;4&lt;/sub&gt;. Because the slope of the melting curve of GeI&lt;sub&gt;4&lt;/sub&gt; abruptly changes at around 3 GPa, in situ synchrotron diffraction measurements were conducted to examine closely the structural changes upon compression at around 3 GPa. The reduced radial distribution functions of the high- and low-pressure liquid states of GeI&lt;sub&gt;4&lt;/sub&gt; share the same feature inherent in the high-pressure (high-density) and low-pressure (low-density) radial distribution functions of liquid SnI&lt;sub&gt;4&lt;/sub&gt;. This feature allows us to introduce local order parameters that we may use to observe the transition. Unlike the transition in liquid SnI&lt;sub&gt;4&lt;/sub&gt;, the transition from the low-pressure to the high-pressure structure seems sluggish. We speculate that the liquid-liquid critical point of GeI&lt;sub&gt;4&lt;/sub&gt; is no longer a thermodynamically stable state and is slightly located below the melting curve. As a result, the structural change is said to be a crossover rather than a transition. The behavior of the local-order parameters implies a metastable extension of the liquid-liquid phase boundary with a negative slope.&#13.

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