Site-selective adsorption of naphthalene-tetracarboxylic-dianhydride on Ag(110): First-principles calculations

TL;DR

This study uses first-principles density functional theory calculations to reveal the site-selective adsorption mechanism of NTCDA on Ag(110), highlighting electron transfer and electrostatic interactions as key factors.

Contribution

It provides the first detailed theoretical explanation of the site-selective adsorption mechanism of NTCDA on Ag(110).

Findings

Adsorption energy in the most stable site is 0.9 eV.

Bonding is driven by electron transfer to the LUMO.

Electrostatic attraction between carboxyl oxygens and silver atoms.

Abstract

The mechanism of adsorption of the 1,4,5,8-naphthalene-tetracarboxylic-dianhydride (NTCDA) molecule on the Ag(110) surface is elucidated on the basis of extensive density functional theory calculations. This molecule, together with its perylene counterpart, PTCDA, are archetype organic semiconductors investigated experimentally over the past 20 years. We find that the bonding of the molecule to the substrate is highly site-selective, being determined by electron transfer to the LUMO of the molecule and local electrostatic attraction between negatively charged carboxyl oxygens and positively charged silver atoms in [1-10] atomic rows. The adsorption energy in the most stable site is 0.9eV. A similar mechanism is expected to govern the adsorption of PTCDA on Ag(110) as well.