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In this geometry optimization, the molecule-substrate interactions are not taken into account. Therefore, the Cu(100) substrate plays a role of just a template for the c(2 × 6)-S structure in the calculation. Although the alkyl-copper interactions are negligible for the standing-up molecular orientation, potential for Cu-S-C angle obviously tends to force the S-C bond to stand up. Since this potential is not considered in the calculation, the resultant tilt angle (37°) should be considered as the maximum.
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