Molecular reorientation in assembled CO structures and contrast inversion in STM

Recent scanning tunneling microscopy experiments [S. Zِphel, J. Repp, G. Meyer, K.-H. Rieder, Chem. Phys. Lett. 310 (1999) 145; A.J. Heinrich, C.P. Lutz, J.A. Gupta, D.M. Eigler, Science 298 (2002) 1381] for CO on Cu(1 1 1) and Cu(2 1 1) surfaces show CO monomers as dark depressions, whereas dimers and trimers appear as bright patterns. The dark image of a monomer has been shown to result from a destructive interference between two tunneling paths [J. Nieminen, E. Niemi, K.-H. Rieder, Surf. Sci. 552 (2004) L47]. In this Letter, we show how switching between tunneling channels within the through molecule path can be induced by reorientation of a molecule. Hence, a destructive interference between through vacuum and through molecule paths can be reversed into constructive interference by manipulating the adsorbate geometry.