Epitaxial growth of CO on NaCl(100) studied by infrared spectroscopy

Abstract

Vibrational spectra of CO physisorbed onto well defined NaCl(100) surfaces were studied using a Fourier transform infrared interferometer. Structures of CO starting from the monolayer to multilayers were explored. At 31.5 K and a CO pressure of 1×10−6 mbar only the monolayer is formed. Polarization measurements confirm our earlier study that the monolayer CO molecules are aligned perpendicular to the NaCl(100) surface. Increasing the CO pressure to 7×10−6 mbar produces multilayer adsorption. The multilayer spectra closely resemble that of α-CO absorption previously reported. The near perfect match of crystal structures and lattice constants of α-CO and NaCl is reasoned to force the epitaxial growth of single crystal multilayers in our experiments. At 22 K the monolayer absorption is at 2155.01 cm−1 with a bandwidth (FWHH) of 0.26 cm−1. The two prominent features in the multilayer spectra at 22 K are assigned to the longitudinal optical (LO) mode at 2142.54 cm−1 and the transverse optical (TO) mode at 2138.51 cm−1. Their frequency separation is a consequence of the lowering of the cubic symmetry of the bulk α-CO crystal by the shape, in the form of thin slabs, of our multilayer samples. Their bandwidths depend on the thickness of the sample and are characterized by a bandwidth parameter of 0.25 cm−1 for the LO mode and 0.85 cm−1 for the TO mode. The relative absorbances of these modes depend on the polarization of the infrared radiation. Theoretical formalism to account for the band splitting and absorption profiles of the infrared absorption is reviewed and applied to our measurements. While many features of our data can be explained by the present theory, further work is required to account for all the experimental results.