jp412651j_si_001.pdf (523.83 kB)
Formation of Chiral Self-Assembled Structures of Amino Acids on Transition-Metal Surfaces: Alanine on Pd(111)
journal contribution
posted on 2014-04-03, 00:00 authored by Mausumi Mahapatra, Luke Burkholder, Yun Bai, Michael Garvey, J. Anibal Boscoboinik, Carol Hirschmugl, Wilfred T. TysoeThe structure and self-assembly of
alanine on Pd(111) is explored using X-ray photoelectron spectroscopy
(XPS), low-energy electron diffraction (LEED), reflection–absorption
infrared spectroscopy (RAIRS), and scanning tunneling microscopy (STM),
and supplemented by density functional theory (DFT) calculations to
explore the stability of the proposed surface structures formed by
adsorbing alanine on Pd(111) and to simulate the STM images. Both
zwitterionic and anionic species are detected using RAIRS and XPS,
while DFT calculations indicate that isolated anionic alanine is significantly
more stable than the zwitterion. This observation is rationalized
by observing dimeric species when alanine is dosed at ∼270
K and then cooled to trap metastable surface structures. The dimers
form due to an interaction between the carboxylate group of anionic
alanine with the NH3+ group of the zwitterion.
Adsorbing alanine at 290 K results in the formation of dimer rows
and tetramers resulting in only short-range order, consistent with
the lack of additional diffraction spots in LEED. The stability of
various structures is explored using DFT, and the simulated STM images
are compared with experiment. This enables the dimer rows to be assigned
to the assembly of anionic-zwitterionic dimers and the tetramer to
the assembly of two dimers in which three of the alanine molecules
undergo a concerted rotation by 30°.