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Realizing a quantum spin liquid (QSL) ground state in a real material is aleading issue in condensed matter physics research. In this pursuit, it iscrucial to fully characterize the structure and influence of defects, as thesecan significantly affect the fragile QSL physics. Here, we perform a variety ofcutting-edge synchrotron X-ray scattering and spectroscopy techniques, and weadvance new methodologies for site-specific diffraction and L-edge Znabsorption spectroscopy. The experimental results along with ourfirst-principles calculations address outstanding questions about the local andlong-range structures of the two leading kagome QSL candidates, Zn-substitutedbarlowite Cu$_3$Zn$_{x}$Cu$_{1-x}$(OH)$_6$FBr and herbertsmithiteCu$_3$Zn(OH)$_6$Cl$_2$. On all length scales probed, there is no evidence thatZn substitutes onto the kagome layers, thereby preserving the QSL physics ofthe kagome lattice. Our calculations show that antisite disorder is notenergetically favorable and is even less favorable in Zn-barlowite compared toherbertsmithite. Site-specific X-ray diffraction measurements of Zn-barlowitereveal that Cu$^{2+}$ and Zn$^{2+}$ selectively occupy distinct interlayersites, in contrast to herbertsmithite. Using the first measured Zn L-edgeinelastic X-ray absorption spectra combined with calculations, we discover asystematic correlation between the loss of inversion symmetry frompseudo-octahedral (herbertsmithite) to trigonal prismatic coordination(Zn-barlowite) with the emergence of a new peak. Overall, our measurementssuggest that Zn-barlowite has structural advantages over herbertsmithite thatmake its magnetic properties closer to an ideal QSL candidate: its kagomelayers are highly resistant to nonmagnetic defects while the interlayers canaccommodate a higher amount of Zn substitution.

Site-Specific Structure at Multiple Length Scales in Kagome Quantum Spin Liquid Candidates