Size effect and odd-even alternation in the melting of single and stacked AgSCn layers: synthesis and nanocalorimetry measurements.

We report a systematic study of melting of layered lamella of silver alkanethiolates (AgSCn). A new synthesis method allows us to independently change the thickness of the crystal in two ways-by modulating chain length (n = 7-18) and by stacking these crystals to a specific layer number (m = 1-10). This method produces magic size lamella, having a well-spaced discrete melting point, Tm, distribution. Nanocalorimetry shows stepwise increases in Tm, as the lamella thickness increases by integer increments of chain length. The relationship between Tm and the inverse thickness follows the linear scaling law of Gibbs-Thomson effect. Layer stacking dramatically changes the degree and nature of size-effect melting. There is odd/even effect in stacked 2, 3, and 4 layers. Tm values of single-layer and multilayer samples do not show noticeable odd/even alternation. We develop a phenomenological model of size effect based on the cumulative excess free energy, G(excess), contributions of four spatially separate regions of the crystal: surface, Ag-S central plane, substrate interface, and interlayer interface. The selective appearance of the odd/even effect is due to the significant stabilization (1.4 kJ/mol) of interlamellae interfaces of odd-chain samples, possibly due to registration/packing. Stabilization occurs only for the mobile lamellae situated close to the free surface, and thus 2-layer samples show the highest degree of stabilization. X-ray diffraction shows that the chains are tilted 18° with respect to the basal plane normal but that the van der Waals gap is 0.3 Å smaller for crystals with odd chains.