Origin of the nonresonant signal in sum-frequency vibrational spectroscopy at the water interface

IF 2.9 3区化学 Q3 CHEMISTRY, PHYSICAL

Physical Chemistry Chemical Physics Pub Date : 2025-10-02 DOI:10.1039/d5cp03270a

Ren-Hui Zheng, Wen-Mei Wei

引用次数: 0

Abstract

We theoretically investigate the origin of the nonresonant sum-frequency vibrational spectroscopy (SFVS) in interfacial water. The ground and excited states of water molecules are calculated using density functional theory (DFT) and time-dependent DFT (TDDFT). Transition moments, including electric and magnetic dipole as well as electric quadrupole terms, are computed. The SFVS from the electric dipole contribution is evaluated considering molecular orientations from neural network-based molecular dynamics simulations. The results demonstrate that the nonresonant SSP SFVS is dominated by the electric quadrupole contribution, with negligible contributions from electric and magnetic dipole terms. Theoretical predictions align well with experimental SFVS measurements, underscoring the importance of quadrupole effects in interfacial spectroscopy.

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水界面和频振动谱中非共振信号的来源

从理论上研究了界面水中非共振和频振动谱（SFVS）的起源。利用密度泛函理论（DFT）和时变DFT （TDDFT）计算了水分子的基态和激发态。跃迁矩，包括电和磁偶极子以及电四极子项，计算。考虑基于神经网络的分子动力学模拟的分子取向，对电偶极子贡献的SFVS进行了评估。结果表明，非谐振SSP SFVS以电四极子贡献为主，电偶极子和磁偶极子项的贡献可以忽略不计。理论预测与实验SFVS测量结果很好地吻合，强调了界面光谱学中四极效应的重要性。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Physical Chemistry Chemical Physics 化学-物理：原子、分子和化学物理

CiteScore

5.50

自引率

9.10%

发文量

2675

审稿时长

2.0 months

期刊介绍： Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.