应用量化计算理解水分子的振动斯塔克效应

引用本文: 赵素品, 谢静. 应用量化计算理解水分子的振动斯塔克效应[J]. 大学化学, 2025, 40(3): 178-185. doi: 10.12461/PKU.DXHX202406024 shu

Citation: Supin Zhao, Jing Xie. Understanding the Vibrational Stark Effect of Water Molecules Using Quantum Chemistry Calculations[J]. University Chemistry, 2025, 40(3): 178-185. doi: 10.12461/PKU.DXHX202406024 shu

应用量化计算理解水分子的振动斯塔克效应

赵素品 ,
谢静 ^,

北京理工大学化学与化工学院, 北京 102488

通讯作者: 谢静,E-mail:jingxie@bit.edu.cn

基金项目:
国家自然科学基金(21903004,22273004)

摘要: 振动斯塔克效应(vibrational Stark effect)是指振动光谱在外加电场作用下发生移动的现象，该效应在现代化学中有广泛的应用。为了增进对振动斯达克效应的理解，本文选择了水的单分子H₂O和二聚体分子(H₂O)₂，通过密度泛函理论计算展示了外加定向电场对这两个分子的振动频率的影响。计算显示，外加定向电场直接影响分子的几何结构、电荷密度、偶极矩、能量，以及振动频率。随着电场强度的增大，H₂O和(H₂O)₂分子的红外振动光谱都出现了收缩现象，即高频的O―H伸缩振动红移，而低频的H―O―H弯曲振动蓝移，这与文献中模拟结果一致。本文为理解振动斯塔克效应提供了一个简单清晰的理论计算案例。

关键词:

English

Understanding the Vibrational Stark Effect of Water Molecules Using Quantum Chemistry Calculations

Supin Zhao ,
Jing Xie ^,

School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 102488, China

Corresponding author: Jing Xie, jingxie@bit.edu.cn

Received Date: 11 June 2024
Revised Date: 15 August 2024
Available Online: 21 February 2025

Abstract: The vibrational Stark effect refers to the infrared spectral lines shifting when exposed to an external electric field. This effect has broad applications in modern chemistry. To facilitate the understanding of the vibrational Stark effect, we selected two water molecules for study, i.e., the monomer H₂O and the dimer (H₂O)₂. Using density functional theory calculations, we investigated the influence of an applied electric field directly affects the targeted molecules' geometry, electron density, dipole moment, energy, and vibrational frequencies. As the field strength increases, both H₂O and (H₂O)₂ exhibits spectral shrink, with a redshift of the high-frequency O―H stretching vibrations and a blueshift of the lower-frequency H―O―H bending vibrations. These findings are consistent with previous simulation results reported in the literature. This work provides a straightforward and clear computational case for understanding the vibrational Stark effect.

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沈阳化工大学材料科学与工程学院沈阳 110142

应用量化计算理解水分子的振动斯塔克效应

通讯作者: 谢静,E-mail:jingxie@bit.edu.cn

English

Understanding the Vibrational Stark Effect of Water Molecules Using Quantum Chemistry Calculations

Corresponding author: Jing Xie, jingxie@bit.edu.cn

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

应用量化计算理解水分子的振动斯塔克效应

通讯作者: 谢静,E-mail:jingxie@bit.edu.cn

English

Understanding the Vibrational Stark Effect of Water Molecules Using Quantum Chemistry Calculations

Corresponding author: Jing Xie, jingxie@bit.edu.cn

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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