基于DFT的间羟基苯甲酸分子表面增强拉曼光谱研究
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摘要
本文研究了间羟基苯甲酸(m-hydroxybenzoic acid,MHBA)的常规拉曼散射(normal Raman scattering,NRS)光谱及其吸附在Ag纳米颗粒上的表面增强拉曼散射(surface-enhanced Raman scattering,SERS)光谱。采用密度泛函理论(density functional theory,DFT),在B3LYP/6-31+G**(C、H、O)/LANL2DZ(Ag)水平上,对MHBA分子进行了几何结构优化,在此基础上计算了MHBA分子的NRS光谱以及其吸附在Ag纳米颗粒上两种不同吸附构型下的SERS光谱,并和实验值进行比较。结果表明,间羟基苯甲酸分子通过羧基与羟基共同吸附构型的计算结果比该分子通过羧基吸附构型的计算结果更符合实验值。最后,利用GaussView可视化软件对其振动模式进行了全面归属。
In this paper,both Normal Raman Scattering(NRS)spectroscopy and the Surface-enhanced Raman Scattering(SERS)spectroscopy that adsorbed on silver nanoparticles of m-hydroxybenzoic acid(MHBA)were researched.At the B3LYP/6-31+G* *(C、H、O)/LANL2DZ(Ag)level,Density Functional Theory(DFT)method was used to optimize molecular configurations of MHBA.Based on optimized structure,the NRS spectroscopy and the SERS spectroscopy by different adsorption configurations of MHBA had been calculated all.Compared with the experimental data,the calculation results using MHBA molecular adsorption configuration through both carboxyl and hydroxyl groups were much more matched with experimental values than those of through carboxyl.At the end,comprehensive assignments of the vibration mode for MHBA were studied by the software of GaussView.
In this paper,both Normal Raman Scattering(NRS)spectroscopy and the Surface-enhanced Raman Scattering(SERS)spectroscopy that adsorbed on silver nanoparticles of m-hydroxybenzoic acid(MHBA)were researched.At the B3LYP/6-31+G* *(C、H、O)/LANL2DZ(Ag)level,Density Functional Theory(DFT)method was used to optimize molecular configurations of MHBA.Based on optimized structure,the NRS spectroscopy and the SERS spectroscopy by different adsorption configurations of MHBA had been calculated all.Compared with the experimental data,the calculation results using MHBA molecular adsorption configuration through both carboxyl and hydroxyl groups were much more matched with experimental values than those of through carboxyl.At the end,comprehensive assignments of the vibration mode for MHBA were studied by the software of GaussView.
引文
[1]邓红霞,郑志文,张晓铭.间羟基苯甲酸合成进展[J].浙江化工,2007,38(3):15-16.(Deng Hongxia,Zheng Zhiwen,Zhang Xiaoming.Development in synthesis of m-hydroxybenzoic acid[J].Zhejiang Chemical Industry,2007,38(3):15-16)
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[7]Furini L N,Constantino C J L,Sanchez-Cortes S,et al.Adsorption of carbendazim pesticide on plasmonic nanoparticles studied by surface-enhanced Raman scattering[J].J Colloid Interf Sci,2016,465:183-189.
[8]刘雅琼,王玉芳.金属银离子与四氯二苯并对二恶英相互作用及其表面增强拉曼光谱的研究[J].光散射学报,2014,26(3):239-244.(Liu Yaqiong,Wang Yufang.A Theory study on the interaction of metallic silver ions and tetrachlorodibenzodioxin and its surface-enhanced Raman spectroscopy[J].The Journal of Light Scattering,2014,26(3):239-244)
[9]Gao S M,Wang H Y,Zhang B M,et al.Surface-enhanced Raman scattering of uracil and uracil dimer on silver by density functional method[J].J Mol Struct,2013,1038:95-100.
[10]Garrido C,Diaz-Fleming G,Campos-Vallette M M.SERS spectrum of gallic acid obtained from a modified silver colloid[J].Spectrochim Acta Part A,2016,163:68-72.
[11]王曼,赵彦英.5-甲基-2-硫代尿嘧啶紫外和振动光谱研究[J].浙江理工大学学报,2013,30(4):609-615.(Wang Man,Zhao Yanying.Research on UV and Vibrational Spectrum of 5-methy-2-thiouracil[J].Journal of Zhejiang SciTech University,2013,30(4):609-615.)
[12]Wu D,Fang Y.Surface-enhanced Raman scattering of a series of n-hydroxybenzoic acids(n=P,M and O)on the silver nano-particles[J].Spectrochim Acta Part A,2004,60(8-9):1845-1852.
[13]Tao Z M,Fang Y.An experimental and theoretical study on the adsorption behaviors of MHBA ions on silver nano-particles[J].J Mol Struct.,2006,797(1-3):40-43.
[14]Lee P C,Meisel D.Adsorption and surface-enhanced Raman of dyes on silver and gold sols[J].J Phys Chem,1982,86(17):3391-3395.
[15]Frisch M J,Trucks G W,Schlegel H B,et al.Gaussian03,Revision 03,Revision B.05,Gaussian,Inc.,Pittsburgh PA,2003.
[2]赵波,卢文庆,吴芸.一种激光倍频新材料-间羟基苯甲酸的初步研究[J].高等学校化学学报,2000,21(4):620-622.(Zhao Bo,Lu Wenqing,Wu Yun.Primary Study on a new kind of second-order nonlinear optical material-m-hydroxybenzoic acid[J].Chem J Chin Universities,2000,21(4):620-622)
[3]Moskovits M.Surface-enhanced spectroscopy[J].Rev Mod Phys,1985,57(3):783-826.
[4]Tian S,Zhou Q,Li C H,et al.Exploring the chemical enhancement of surface-enhanced Raman scattering with a designed silver/silica cavity substrate[J].J Phys Chem C,2013,117(1):556-563.
[5]Chen Y F,Yang J,Li Z L,et al.Experimental and density functional theory study of Raman and SERS spectra of 5-amino-2-mercaptobenzimidazole[J].Spectrochim Acta Part A,2016,153:344-348.
[6]Chen Y,Chen S J,Li S,et al.SERS and DFT study of phydroxybenzoic acid adsorbed on colloidal silver particles[J].Cell Mol Biol,2015,61(5):11-15.
[7]Furini L N,Constantino C J L,Sanchez-Cortes S,et al.Adsorption of carbendazim pesticide on plasmonic nanoparticles studied by surface-enhanced Raman scattering[J].J Colloid Interf Sci,2016,465:183-189.
[8]刘雅琼,王玉芳.金属银离子与四氯二苯并对二恶英相互作用及其表面增强拉曼光谱的研究[J].光散射学报,2014,26(3):239-244.(Liu Yaqiong,Wang Yufang.A Theory study on the interaction of metallic silver ions and tetrachlorodibenzodioxin and its surface-enhanced Raman spectroscopy[J].The Journal of Light Scattering,2014,26(3):239-244)
[9]Gao S M,Wang H Y,Zhang B M,et al.Surface-enhanced Raman scattering of uracil and uracil dimer on silver by density functional method[J].J Mol Struct,2013,1038:95-100.
[10]Garrido C,Diaz-Fleming G,Campos-Vallette M M.SERS spectrum of gallic acid obtained from a modified silver colloid[J].Spectrochim Acta Part A,2016,163:68-72.
[11]王曼,赵彦英.5-甲基-2-硫代尿嘧啶紫外和振动光谱研究[J].浙江理工大学学报,2013,30(4):609-615.(Wang Man,Zhao Yanying.Research on UV and Vibrational Spectrum of 5-methy-2-thiouracil[J].Journal of Zhejiang SciTech University,2013,30(4):609-615.)
[12]Wu D,Fang Y.Surface-enhanced Raman scattering of a series of n-hydroxybenzoic acids(n=P,M and O)on the silver nano-particles[J].Spectrochim Acta Part A,2004,60(8-9):1845-1852.
[13]Tao Z M,Fang Y.An experimental and theoretical study on the adsorption behaviors of MHBA ions on silver nano-particles[J].J Mol Struct.,2006,797(1-3):40-43.
[14]Lee P C,Meisel D.Adsorption and surface-enhanced Raman of dyes on silver and gold sols[J].J Phys Chem,1982,86(17):3391-3395.
[15]Frisch M J,Trucks G W,Schlegel H B,et al.Gaussian03,Revision 03,Revision B.05,Gaussian,Inc.,Pittsburgh PA,2003.