基于密度泛函理论对团簇CrPS_(4)的光谱分析  

Spectral analysis of clustered CrPS_(4)based on density functional theory

作　　者：方志刚[1] 刘立娥 吴庭慧 宋静丽 原琳 魏代霞 FANG Zhigang;LIU Li′e;WU Tinghui;SONG Jingli;YUAN Lin;WEI Daixia(School of Chemical Engineering,University of Science and Technology Liaoning,Anshan,Liaoning 114051,China)

机构地区：[1]辽宁科技大学化学工程学院,辽宁鞍山114051

出　　处：《贵州师范大学学报（自然科学版）》2024年第3期1-8,共8页Journal of Guizhou Normal University：Natural Sciences

基　　金：国家自然科学基金重点项目(51634004);国家级大学生创新创业训练计划(202310146025、202310146026、202310146027、202210146008、202210146009、202210146011);辽宁省大学生创新创业训练计划项目(S202310146046)。

摘　　要：为快速、高效得到物质的谱图数据,利用计算化学方法,根据拓扑学原理,利用密度泛函理论,对团簇CrPS_(4)10种优化构型的红外光谱、拉曼光谱、偶极矩以及极化率进行了分析,并利用构型2^((4))的理论红外谱图与前人所得实际光谱图进行了对比。结果显示:CrPS_(4)红外光谱的波峰大致分布在300~700 cm^(-1)范围内,拉曼光谱的波峰范围主要分布在200~700 cm^(-1)范围内;团簇CrPS_(4)振动形式为伸缩振动时,其对入射光的吸收强度较大;在频率较低的波段,CrPS_(4)更易发生红外吸收,在频率较高的波段,更易发生拉曼散射;总偶极矩的排列顺序为2^((2))>6^((4))>4^((2))>3^((2))>3^((4))>4^((4))>1^((2))>2^((4))>5^((4))>1^((4)),偶极矩越大,红外活性越强;极化率大小关系满足5^((4))<1^((4))<6^((4))<4^((4))<3^((4))<1^((2))<2^((4))<2^((2))<3^((2))<4^((2)),极化率越大,拉曼活性越强;所有构型的3大主轴中,XX轴的极化率均大于YY轴与ZZ轴;构型2^((4))的理论光谱图与实际结果对比发现,两者光谱图波峰频率基本吻合,实验与理论分析互为补充。In order to obtain the spectral data of the substances quickly and efficiently,the infrared spectra,Raman spectra,dipole moments,and polarizabilities of 10 optimized configurations of clustered CrPS_(4)have been analyzed in this paper by using computational chemistry methods and using density-functional theory,based on topological principles.By using the theoretical infrared spectra of configuration 2^((4)),they have been compared with the actual spectra obtained by the previous studies.The following conclusions were obtained:The peaks of the Infrared spectrum of CrPS_(4)are roughly distributed in the range of 300~700 cm^(-1),while the peak range of the Raman spectrum is mainly distributed in the range of 200~700 cm^(-1);The intensity of absorption of incident light is greater when the cluster CrPS_(4)vibration is in the form of telescopic vibration;CrPS_(4)is more susceptible to infrared absorption at lower frequency bands and Raman scattering at higher frequency bands;The total dipole moments are ranked in the order of 2^((2))>6^((4))>4^((2))>3^((2))>3^((4))>4^((4))>1^((2))>2^((4))>5^((4))>1^((4)),and the larger the dipole moments are,the more infrared-active they are;The polarizability size relationship satisfies 5^((4))<1^((4))<6^((4))<4^((4))<3^((4))<1^((2))<2^((4))<2^((2))<3^((2))<4^((2)),and the larger the polarizability,the stronger the Raman activity;The polarization rate of the XX axis is greater than that of the YY and ZZ axes for all configurations of the 3 major spindles;Comparison of the theoretical spectrogram of configuration 2^((4))with the actual results reveals that the wave peak frequencies of the two spectrograms are basically in agreement,and the experimental and theoretical analyses are complementary to each other.

关 键 词：光谱 密度泛函理论 红外光谱 拉曼光谱 极化率 偶极矩 

分 类 号：O641.12[理学—物理化学]