Journal
JOURNAL OF PHYSICAL CHEMISTRY B
Volume 110, Issue 3, Pages 1271-1276Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jp0541314
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The molecular architecture of acridine-9-carboxylic acid (ACA) grown on Ag (111) by physical vapor deposition was characterized by using UHV-STM and XPS. At lower coverage, ACA molecules exist in a 2-d gas phase on the surface at room temperature. With increased coverage (> 0.4 ML), ACA molecules self-organize into distinctive adlayer structures that are correlated with underlying substrate morphology. On step-free Ag (111) regions, ACA molecules form large islands in coexistence with the 2-d ACA gas. These islands are commensurate with the Ag (111) substrate, indexed as (40, 24) in matrix notation, and can exceed 100 nm in size. There are two nonequivalent ACA molecules in each unit cell. XPS core level measurements reveal a hydrogen-bonding interaction between ACA molecules, with the ring nitrogen acting as the H-bond acceptor and the carboxyl proton acting as the H-bond donor. A structural model for this phase consists of chains of ACA molecules linked by head-to-tail hydrogen bonds along the substrate [1 (1) over bar0] direction. Alternating ACA tilting angles account for the two nonequivalent ACA molecules and the observed high packing density. Completely different molecular arrangements are observed on Ag (111) surface regions roughened by a higher density of crystallographic steps (terrace widths <= 6nm). Pairs of ACA molecules arrange in a zigzag pattern in a (122, 65) overlayer structure with a diluted packing density. The structural model for this lower density phase consists of carboxyl-carboxyl linked ACA dimers in a flat-lying molecular orientation.
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