Revealing the interfacial water structure on a <i>p</i>-nitrobenzoic acid specifically adsorbed Au(111) surface

Fang, Yuan; Hu, Ren; Ye, Jinyu; Qu, Haiyan; Zhou, Zhi‐You; Duan, Sai; Tian, Zhong‐Qun; Xu, Xin

doi:10.1039/d3sc00473b

Cited by 4 publications

(4 citation statements)

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“…Among them, an Ion-5MW configuration, in which the proton in the carboxyl group automatically dissociates to form PNBA − and the first water layer forms fused four-and five-membered rings, can give similar measured SEIRAS spectra in the characteristic vibrational regions of 1000−1800 cm −1 and 3000−3800 cm −1 (Figure 6b). 62 Thus, with the close combination of EC-STM and SEIRAS, theoretical simulations and experimental measurements revealed an interfacial water structure with unusually small rings in the specific adsorption electrochemical interfaces. The identified particular water structure could be more robust in electrochemistry than our expectation, extending our understanding of the electric double layer.…”

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confidence: 85%

“…Owing to the sensitivity to the PNBA and water molecules, surface-enhanced infrared absorption spectroscopy (SEIRAS) was adopted to reveal the interfacial structure. , Based on the identified p (3 × 5)-2PNBA from the EC-STM image, SEIRAS spectra of several possible interfacial configurations were calculated. Among them, an Ion-5MW configuration, in which the proton in the carboxyl group automatically dissociates to form PNBA – and the first water layer forms fused four- and five-membered rings, can give similar measured SEIRAS spectra in the characteristic vibrational regions of 1000–1800 cm –1 and 3000–3800 cm –1 (Figure b) . Thus, with the close combination of EC-STM and SEIRAS, theoretical simulations and experimental measurements revealed an interfacial water structure with unusually small rings in the specific adsorption electrochemical interfaces.…”

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confidence: 99%

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confidence: 99%

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Accurate Simulations of Scanning Tunneling Microscope: Both Tip and Substrate States Matter

Duan

2023

J. Phys. Chem. Lett.

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Scanning tunneling microscope (STM) provides an atomic-scale characterization tool. To this end, high-resolution measurements and accurate simulations must closely cooperate. Emerging experimental techniques, e.g., substrate spacers and tip modifications, suppress metallic couplings and improve the resolution. On the other hand, development of STM simulation methods was inactive in the past decade. Conventional simulations focus on the electronic structure of the substrate, often overlooking detailed descriptions of the tip states. Meanwhile, the overwhelming usage of periodic boundary conditions ensures effective simulations of only neutral systems. In this Perspective, we highlight the recent progress that takes the effects of both tip and substrate into account under either Tersoff−Hamann or Bardeen's approximation, which provides an accurate analysis of measured high-resolution STM results, uncovers underlying concepts, and rationally designs experimental protocols for important chemical systems. We hope this Perspective will stimulate broad interest in advanced STM simulations, highlighting the way forward for STM investigations that involve complex geometrical and electronic structures.

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Accurate Simulations of Scanning Tunneling Microscope: Both Tip and Substrate States Matter

Duan

2023

J. Phys. Chem. Lett.

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“…In the past few decades, scientists have ventured into the mysteries of these interfacial interactions, armed with diverse cutting-edge techniques. These methodologies, ranging from X-ray scattering and X-ray absorption spectroscopy (XAS) to infrared spectroscopy (IR), sum frequency generation spectroscopy (SFG), , and Raman spectroscopy, , have illuminated the nuanced arrangements of O–H bonds at various surfaces and under different applied potentials. The insights gained from these investigations hold the key to unlocking a deeper understanding of electrochemical processes and water-related phenomena across a breadth of disciplines.…”

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confidence: 99%

Modeling Vibrational Sum Frequency Generation Spectra of Interfacial Water on a Gold Surface: The Role of the Fermi Resonance

Shen,

Chen,

Zou

et al. 2024

J. Phys. Chem. B

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Studying the hydrogen bonding structure of H 2 O at the metal-water interface is a highly complex yet fascinating endeavor. The intricate interactions and diverse orientations of water molecules on metal surfaces with varying potentials pose a significant challenge in elucidating the coupling between O−H stretching and H−O−H bending modes. In this study, we employed DFT-MD simulation to explore how the orientation of interfacial water molecules changes with the applied potential on the Au(111) surface. Based on the surfacespecific velocity-velocity correlation function (ssVVCF) formula, we calculated vibrational sum frequency generation (VSFG) spectra for the O−H stretches. We found that three assigned peaks (∼3300, ∼3450, and 3650 cm −1 ) shifted toward lower frequencies as the potential moved toward more negative values. Our results align remarkably well with experimental Raman spectroscopy data. Notably, our VSFG analysis revealed a significant change in the VSFG spectra of the hydrogen-bonded O−H groups (∼3300 cm −1 ), switching from a negative to a positive sign with decreasing potential. This alteration suggests a substantial change in the orientation of these low-frequency O−H groups owing to their increased interactions with the Au surface. In contrast, the orientations of both the high-frequency O−H groups (∼3450 cm −1 ) and the dangling O−H groups (∼3650 cm −1 ) remained unaffected by the applied potentials. Furthermore, our analysis of the decomposed vibrational density of states (VDOS) for the H−O−H bending mode uncovered the coupling between the H−O−H bending and O−H stretching vibrations, known as the Fermi resonance. Our work suggests that the H−O−H bending vibration becomes restricted when water molecules transition from the ″one-H-down″ to the ″two-H-down″ conformation, leading to a redshift in the O−H stretching vibration through the Fermi resonance. By constructing the VSFG and decomposed VDOS spectra, we gained valuable insights into the structural changes that Raman spectra alone cannot fully interpret. Specifically, our analysis revealed the critical role of the Fermi resonance effect in shaping the spectroscopic signature of interfacial water molecules on the Au(111) surface.

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Experimental characterization technique to probe interfacial water

Hu,

Huang,

Zhou

et al. 2024

Journal of Catalysis

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Revealing the interfacial water structure on a p-nitrobenzoic acid specifically adsorbed Au(111) surface

Abstract: The detailed structure of water layer in the inner Helmhotz plane of the solid/aqueous solution interface is closely related to the electrochemical and catalytic performances of the electrode materials. While...

Cited by 4 publications

References 53 publications

Accurate Simulations of Scanning Tunneling Microscope: Both Tip and Substrate States Matter

Accurate Simulations of Scanning Tunneling Microscope: Both Tip and Substrate States Matter

Modeling Vibrational Sum Frequency Generation Spectra of Interfacial Water on a Gold Surface: The Role of the Fermi Resonance

Experimental characterization technique to probe interfacial water

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