Benzene adsorbed on Si(001): The role of electron correlation and finite temperature

Abstract

van der Waals energy-corrected density functional theory (DFT + vdW) as well as the exact exchange with electron correlation in the random-phase approximation are used to study the adsorption of benzene on the Si(001) surface with respect to two controversial adsorption structures (termed "butterfly" and "tight bridge"). Our finding that the tight-bridge structure is energetically favored over the butterfly structure agrees with standard DFT but conflicts with previous vdW-inclusive calculations. However, the inclusion of zero-point energy and thermal vibrations reverses the stability of the two structures with increasing temperature. Our results provide an explanation for the recent experimental observation that both structures coexist at room temperature.