Ab initio theoretical study of substituted dicarboxylic acids adsorbed on GaAs surfaces: correlation between microscopic properties and observed electrical behavior.

Five substituted tartaric acid derivatives are studied using density functional theory, both isolated and adsorbed onto an oxidized GaAs cluster, to model molecular layers on semiconductor surfaces. The structures, energies, and electronic properties are computed to clarify the interactions responsible for the electric behavior of the modified surfaces, used in semiconductor/metal junction devices. The chemical structure of the molecule/GaAs adducts is optimized ab initio and discussed for the first time. A strong binding scheme is found, providing useful insights about the microscopic structure of the molecular layer. A widely used model based on molecular dipole layers is discussed and verified, by computing the dipole moment for the isolated systems and estimating the charge separation in the adducts; moreover the molecular orbitals energies are analyzed and correlated to the experimental measures of the modified surface electron affinity.