We present photo-excitation of ultra-long-range Rydberg molecules as a probe of spatial correlations in quantum gases. Rydberg molecules can be created with well-defined internuclear spacing, set by the radius of the outer lobe of the Rydberg electron wavefunction $R_n$. By varying the principal quantum number $n$ of the target Rydberg state, the molecular excitation rate can be used to map the pair-correlation function of the trapped gas $g^{(2)}(R_n)$. We demonstrate this with ultracold Sr gases and probe pair-separation length scales ranging from $R_n = 1400 - 3200$ $a_0$, which are on the order of the thermal de Broglie wavelength for temperatures around 1 $mu$K. We observe bunching for a single-component Bose gas of $^{84}$Sr and anti-bunching due to Pauli exclusion at short distances for a polarized Fermi gas of $^{87}$Sr, revealing the effects of quantum statistics.
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