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The unique mechanical properties of the thiol monolayer are described in earlier work [18]. Upon close inspection, their effort can be seen as a small hysteresis loop in the region of the loading curves within about 10 Å of the initial contact (see Fig. 1). The Hertzian fit slightly deviates from the loading curve in this region.
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The thiol monolayer chemically changes the Au surface, as evidenced by the removal of the herringbone reconstruction of the clean Au(111) surface by monolayer adsorption (Poirier G. E., Pylant E. D., Science, 1996, 272, 1145). Thus, the level of stress on the Au interfacial surface is changed and this could play a subtle role in our mechanical measurements. However, we have assumed that this would affect all measurements the same and would not appreciably change the scaling that we observe with respect to probe-tip radius..
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