TY - JOUR

T1 - Coverage-Induced Orientation Change

T2 - CO on Ir(111) Monitored by Polarization-Dependent Sum Frequency Generation Spectroscopy and Density Functional Theory

AU - Li, Xia

AU - Pramhaas, Verena

AU - Rameshan, Christoph

AU - Blaha, Peter

AU - Rupprechter, Günther

N1 - Publisher Copyright: Copyright © 2020 American Chemical Society.

PY - 2020/7/30

Y1 - 2020/7/30

N2 - Polarization-dependent sum frequency generation (SFG) spectroscopy was applied to study the adsorption of carbon monoxide (CO) on the well-ordered (annealed) Ir(111) single-crystal surface at various CO coverages. Coverage was adjusted by varying the substrate temperature (300-575 K) and/or gas pressure (10-7 to 1.0 mbar). Under all conditions investigated, only a single absorption band at 2038-2094 cm-1 was observed, characteristic of linearly bonded (on-top) CO. Using different polarizations, PPP and SSP spectra were acquired with a high signal-to-noise ratio, whereby tilt angles of CO on Ir(111) could be determined for the first time by SFG. It was found that not only the vibrational frequency of on-top CO but also the tilt angle was strongly coverage-dependent. The higher the coverage was, the larger the vibrational frequency and the tilt angle were. At about 0.7 ML coverage, a CO tilt angle of at least 20° was observed, which is in good agreement with density functional theory (DFT) calculations. In addition, the molecular hyperpolarizability ratio (R) of CO (at 0.13 ML in UHV) was determined to be 0.08. Based on the combined SFG/DFT results, it may change to 0.29 at 0.77 ML coverage.

AB - Polarization-dependent sum frequency generation (SFG) spectroscopy was applied to study the adsorption of carbon monoxide (CO) on the well-ordered (annealed) Ir(111) single-crystal surface at various CO coverages. Coverage was adjusted by varying the substrate temperature (300-575 K) and/or gas pressure (10-7 to 1.0 mbar). Under all conditions investigated, only a single absorption band at 2038-2094 cm-1 was observed, characteristic of linearly bonded (on-top) CO. Using different polarizations, PPP and SSP spectra were acquired with a high signal-to-noise ratio, whereby tilt angles of CO on Ir(111) could be determined for the first time by SFG. It was found that not only the vibrational frequency of on-top CO but also the tilt angle was strongly coverage-dependent. The higher the coverage was, the larger the vibrational frequency and the tilt angle were. At about 0.7 ML coverage, a CO tilt angle of at least 20° was observed, which is in good agreement with density functional theory (DFT) calculations. In addition, the molecular hyperpolarizability ratio (R) of CO (at 0.13 ML in UHV) was determined to be 0.08. Based on the combined SFG/DFT results, it may change to 0.29 at 0.77 ML coverage.

UR - http://www.scopus.com/inward/record.url?scp=85091847188&partnerID=8YFLogxK

U2 - 10.1021/acs.jpcc.0c04986

DO - 10.1021/acs.jpcc.0c04986

M3 - Article

AN - SCOPUS:85091847188

VL - 124.2020

SP - 18102

EP - 18111

JO - Journal of Physical Chemistry C

JF - Journal of Physical Chemistry C

SN - 1932-7447

IS - 33

ER -