期刊
JOURNAL OF PHYSICAL CHEMISTRY C
卷 120, 期 6, 页码 3428-3437出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpcc.5b12387
关键词
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资金
- Austrian Science Fund (FWF) [P24666-N20, I937-N19]
- German Research Foundation (DFG) [ZH 63/17-1]
- Austrian Science Fund (FWF) [P24666] Funding Source: Austrian Science Fund (FWF)
The focus of the present article is on understanding the insight that X-ray photoelectron spectroscopy (XPS) measurements can provide when studying self assembled monolayers. Comparing density functional theory calculations to experimental data on deliberately chosen model systems, we show that both the chemical environment and electrostatic effects arising from a superposition of molecular dipoles influence the measured core-level binding energies to a significant degree. The crucial role of the often overlooked electrostatic effects in polar self-assembled monolayers (SAMs) is unambiguously demonstrated by changing the dipole density through varying the SAM coverage. As a consequence of this effect, care has to be taken when extracting chemical information from the XP spectra of ordered organic adsorbate layers. Our results, furthermore, imply that XPS is a powerful tool for probing local variations in the electrostatic energy in nanoscopic systems, especially in SAMs.
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