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

IF 2.8 2区 化学 Q3 CHEMISTRY, PHYSICAL The Journal of Physical Chemistry B Pub Date : 2024-06-26 DOI:10.1021/acs.jpcb.4c02043
Hujun Shen*, Ling Chen, Xuefeng Zou and Qingqing Wu, 
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Abstract

Studying the hydrogen bonding structure of H2O 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 surface-specific 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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金表面界面水振动和频谱生成模型:费米共振的作用
研究金属-水界面上 H2O 的氢键结构是一项非常复杂而又引人入胜的工作。水分子在不同电位的金属表面上的相互作用错综复杂,取向也各不相同,这给阐明 O-H 伸展和 H-O-H 弯曲模式之间的耦合带来了巨大挑战。在本研究中,我们采用 DFT-MD 模拟来探索界面水分子的取向如何随着金(111)表面的外加电势而变化。根据表面特定速度-速度相关函数(ssVVCF)公式,我们计算了 O-H 伸展的振动和频谱(VSFG)。我们发现,随着电位向更负的值移动,三个指定峰(∼3300、∼3450 和 3650 cm-1)向更低的频率移动。我们的结果与拉曼光谱实验数据非常吻合。值得注意的是,我们的 VSFG 分析表明,氢键 O-H 基团的 VSFG 光谱(∼3300 cm-1)发生了显著变化,随着电位的降低从负号转为正号。这种变化表明这些低频 O-H 基团与金表面的相互作用增加,从而使其取向发生了重大变化。相比之下,高频 O-H 基团(∼3450 cm-1)和悬垂 O-H 基团(∼3650 cm-1)的取向不受所施加电位的影响。此外,我们对 H-O-H 弯曲模式的分解振动状态密度(VDOS)进行了分析,发现了 H-O-H 弯曲振动与 O-H 拉伸振动之间的耦合,即费米共振。我们的研究表明,当水分子从″一H-下″构象转变为″二H-下″构象时,H-O-H弯曲振动会受到限制,从而导致O-H伸缩振动通过费米共振发生重移。通过构建 VSFG 和分解 VDOS 光谱,我们获得了有关结构变化的宝贵见解,而这些见解仅靠拉曼光谱是无法完全解释的。具体来说,我们的分析揭示了费米共振效应在形成金(111)表面界面水分子光谱特征方面的关键作用。
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来源期刊
CiteScore
5.80
自引率
9.10%
发文量
965
审稿时长
1.6 months
期刊介绍: An essential criterion for acceptance of research articles in the journal is that they provide new physical insight. Please refer to the New Physical Insights virtual issue on what constitutes new physical insight. Manuscripts that are essentially reporting data or applications of data are, in general, not suitable for publication in JPC B.
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