密度泛函理论研究银上吸附对巯基吡啶的SERS化学增强效应

引用本文: 吴元菲, 李明雪, 周剑章, 吴德印, 田中群. 密度泛函理论研究银上吸附对巯基吡啶的SERS化学增强效应[J]. 物理化学学报, 2017, 33(3): 530-538. doi: 10.3866/PKU.WHXB201611211 shu

Citation: WU Yuan-Fei, LI Ming-Xue, ZHOU Jian-Zhang, WU De-Yin, TIAN Zhong-Qun. Density Functional Theoretical Study on SERS Chemical Enhancement Mechanism of 4-Mercaptopyridine Adsorbed on Silver[J]. Acta Physico-Chimica Sinica, 2017, 33(3): 530-538. doi: 10.3866/PKU.WHXB201611211 shu

密度泛函理论研究银上吸附对巯基吡啶的SERS化学增强效应

厦门大学化学化工学院化学系, 固体表面国家重点实验室, 能源材料化学协同创新中心, 福建厦门 361005
基金项目:
国家自然科学基金（21273182，21533006，21373172）资助项目

摘要: 基于密度泛函理论计算和拉曼光谱理论分析，我们研究了对巯基吡啶（4MPY）分子的拉曼光谱和其在银上的表面增强拉曼光谱（SERS），并进一步探讨了SERS与界面吸附结构、异构化、质子化和氢键作用以及低能激发态的关系。首先，我们对两种分子异构体的相对稳定性和拉曼光谱进行了理论分析。在此基础上，进而研究了该分子与不同银簇作用时的拉曼光谱，结果表明，4MPY以巯基硫与银簇作用形成强的Ag-S键，导致拉曼光谱的线型不依赖于所选银簇的大小。接着我们考虑了吡啶氮端作用的两种情况。（1）当4MPY-银簇复合物同时以吡啶氮与水簇或水合质子簇形成氢键时，结果表明吡啶环的部分振动频率随氢键和质子化发生蓝移。（2）当考虑吡啶氮与银簇作用时，吡啶环三角畸变振动发生蓝移。上述情况不仅解释了实验观测的振动频率变化，而且表明了化学环境改变对相对拉曼强度的影响。最后，我们计算了当对巯基吡啶分子以单端或双端与银簇作用，在考虑激发光与低能激发态的能量匹配时，拉曼光谱强度与低能激发态的关系。计算结果表明，在双端吸附构型下，与吡啶氮成键的银簇受激发产生电荷转移态，不仅导致吡啶环v₁₂、v₁和v_8a振动的拉曼信号增强，而且选择性地增强吡啶环C-H面内对称弯曲振动v_9a的拉曼信号。

关键词:

English

Density Functional Theoretical Study on SERS Chemical Enhancement Mechanism of 4-Mercaptopyridine Adsorbed on Silver

Department of Chemistry, College of Chemistry and Chemical Engineering, State Key Laboratory of Physical Chemistry of Solid Surfaces and Collaborative Innovation Center for Energy Materials Chemistry, Xiamen University, Xiamen 361005, Fujian Province, P. R. China
Received Date: 02 August 2016
Revised Date: 21 November 2016
Fund Project:
The project was supported by the National Natural Science Foundation of China (21273182,21533006,21373172)

Abstract: Surface-enhanced Raman spectroscopy (SERS) is one of the most powerful techniques for obtaining fingerprint information on molecules adsorbed on coinage metal surfaces. Its detection sensitivity has reached the single-molecule level. On the basis of density functional theoretical (DFT) calculations and Raman scattering theory, we investigated the normal Raman spectra of two isomers and surface-enhanced Raman scattering (SERS) spectra of 4-mercaptopyridine (4MPY) adsorbed on silver. The results aided us in uncovering the relationships between normal Raman spectra and SERS spectra and adsorption configuration, tautomerization, protonation, and hydrogen bonding interactions as well as low-lying excited states. First, we compared the relative stability and normal Raman spectra of two isomers of 4MPY in the gas phase and aqueous solution with a solvent model similar to the solvation model of density (SMD). We then studied the Raman spectra of 4MPY interacting with silver clusters. Our results indicate that the Raman spectra were not dependent on the size of the silver clusters, owing to the formation of strong Ag-S bonds. We also considered two cases of Nend interaction in the 4MPY-Ag₅ complex. (1) For the hydrogen bond interaction between the nitrogen in 4MPY and water clusters or hydrated proton clusters, the theoretical results indicated that the vibrational frequencies of the pyridine ring increase. (2) For the interaction of the 4MPY-Ag₅ complex with a silver cluster Ag₄ through the lone-paired orbital in nitrogen of the pyridine ring, the theoretical results further revealed that the vibrational frequency shift is in good agreement with SERS peaks reported in the literature. Finally, our calculated results focused on the relationship between the Raman spectra and the charge transfer mechanism when the excitation photonic energy matches the transition energy of low-lying excited states in single-end and double-end adsorption configuration. Particularly for the case of the double-end adsorption configuration, the charge transfer states from the excitation from the silver cluster binding to the pyridine ring not only enhance the Raman signals of v₁₂, v₁, and v_8a modes, but also selectively enhance the Raman signal of the v_9a mode associated with the symmetric C-H in-plane bending vibration.

Key words:

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密度泛函理论研究银上吸附对巯基吡啶的SERS化学增强效应

English

Density Functional Theoretical Study on SERS Chemical Enhancement Mechanism of 4-Mercaptopyridine Adsorbed on Silver

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中国化学会秘书处

密度泛函理论研究银上吸附对巯基吡啶的SERS化学增强效应

English

Density Functional Theoretical Study on SERS Chemical Enhancement Mechanism of 4-Mercaptopyridine Adsorbed on Silver

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

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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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