苯甲酸和山梨酸混合物的太赫兹吸收峰形成机理解析

doi:10.3964/j.issn.1000-0593(2025)07-1848-09

Abstract
References
Related Citation (15)

Download: PDF (13940 KB)
Export: BibTeX | EndNote (RIS)

Abstract This study focuses on benzoic acid and sorbic acid, using a terahertz time-domain spectroscopy (Terahertz Time-Domain Spectroscopy, THz-TDS) system to measure the experimental spectra of their pure substances and mixed pellets in the 0.5~2.2 THz range.After preprocessing the spectral data, the two substances' terahertz (Terahertz, THz) absorption spectra were obtained. The qualitative identification of the above two substances can be accurately achieved based on the peak positions of the characteristic absorption peaks in the absorption spectra. In this paper, the dimer cluster configurations of the benzoic acid and sorbic acid mixture were constructed using the Genmer component. Structural optimizations, frequency calculations, and screening were conducted for their single molecules, unit cells, and mixture clusters using density functional theory (DFT). The potential energy distribution was used to analyze the vibration modes of the characteristic absorption peaks. Combining the simulated spectra with two interaction visualization methods—Independent Gradient Model based on Hirshfeld atom partitioning (IGMH) and the Interaction Region Indicator (IRI)—the vibration modes of abnormal absorption peaks in the mixed pellet were identified. The molecular and intermolecular interaction features were also visualized. The study found that the special absorption peaks in the simulated spectra of the mixture cluster configuration were caused by hydrogen bond vibrations between molecules. This further illustrates that the characteristic absorption peaks of benzoic acid, sorbic acid, and their mixtures in the terahertz frequency range mainly originate from collective vibration modes induced by intermolecular hydrogen bonds and intramolecular chemical bonds. By constructing and screening cluster configurations of mixed systems, this work deeply investigates the causes of characteristic absorption peaks in the terahertz absorption spectra of mixtures. It highlights the impact of intramolecular and intermolecular interactions and hydrogen bond effects on absorption peaks. This study introduces a novel method for characterizing crystal structures, significantly enhancing the accuracy and reliability of spectral interpretation for mixed systems. It also lays a foundation for subsequent quantitative analyses based on spectral data.

Key words：Terahertz time-domain spectroscopy;Cluster configuration;Characteristic absorption peaks;Mechanism analysis

Received: 2024-09-08 Accepted: 2025-02-18

ZTFLH:

O433.4

Corresponding Authors: YAN Fang E-mail: 0472yanfang@163.com

Cite this article:

LI Wen-wen,YAN Fang,LIU Yang-shuo. A Mechanistic Analysis of Terahertz Absorption Peak Formation in Benzoic Acid and Sorbic Acid Mixtures[J]. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2025, 45(07): 1848-1856.

URL:

https://www.gpxygpfx.com/EN/10.3964/j.issn.1000-0593(2025)07-1848-09 OR https://www.gpxygpfx.com/EN/Y2025/V45/I07/1848

[1] WANG Ying-ying, WANG Li-ping, LI Tian, et al(王莹莹, 汪丽平, 李恬, 等). Acta Optica Sinica(光学学报), 2019, 39(10): 1030003.
[2] YIN Xian-hua, LI Jing-tong, CHEN Hui-cong, et al(殷贤华, 李镜彤, 陈慧聪, 等). Laser & Optoelectronics Progress(激光与光电子学进展), 2023, 60(9): 0930005.
[3] Li Y, Qin B, Zheng J, et al. Optik, 2021, 241: 167063.
[4] Tu S, Wang Z, Zhang W, et al. Infrared Physics & Technology, 2021, 119: 103950.
[5] ZHENG Zhuan-ping, FAN Wen-hui, YAN Hui, et al(郑转平, 范文慧, 闫慧, 等). Spectroscopy and Spectral Analysis(光谱学与光谱分析), 2013, 33(3): 582.
[6] LI Tian-ying, LI Chun, ZHANG Long, et al(李天莹, 李春, 章龙, 等). Spectroscopy and Spectral Analysis(光谱学与光谱分析), 2021, 41(1): 100.
[7] YAN Fang, LIU Tong-hua, ZHANG Jun-lin(燕芳, 刘同华, 张俊林). Acta Optica Sinica(光学学报), 2022, 42(5): 0530001.
[8] Dorney T D, Baraniuk R G, Mittleman D M. Journal of the Optical Society of America A—Optics Image Science & Vision, 2001, 18(7): 1562.
[9] Duvillaret L, Garet F, Coutaz J L. IEEE Journal of Selected Topics in Quantum Electronics, 1996, 2(3): 739.
[10] Groom C R, Bruno I J, Lightfoot M P, et al. Acta Crystallographica Section B: Structural Science, Crystal Engineering and Materials, 2016, 72(2): 171.
[11] Stephens P J, Devlin F J, Chabalowski C F, et al. The Journal of Physical Chemistry, 1994, 98(45): 11623.
[12] Grimme S, Antony J, Ehrlich S, et al. The Journal of Chemical Physics, 2010, 132(15): 154104.
[13] ZHU Zhong-jie, REN Guan-hua, CHENG Chao, et al(朱中杰, 任冠华, 成超, 等). Chinese Journal of Lasers(中国激光), 2019, 46(6): 0614017.
[14] Lu T. Molclus Program, Version 1.12.2023. http://www.keinsci.com/research/molclus.html.
[15] Stewart J J P. MOPAC2024. USA: Colorado Springs, CO. Stewart, Stewart Computational Chemistry, 2024. http: //OpenMOPAC.net.
[16] Jamróz M H. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2013, 114: 220.
[17] Humphrey W, Dalke A, Schulten K. Journal of Molecular Graphics, 1996, 14(1): 33.
[18] Lu T, Chen Q. Journal of Computational Chemistry, 2022, 43(8): 539.
[19] Johnson E R, Keinan S, Mori-Sánchez P, et al. Journal of the American Chemical Society, 2010, 132(18): 6498.
[20] Lu T, Chen Q. Visualization Analysis of Weak Interactions in Chemical Systems, in: Yáñez M, Boyd R J. (Eds.), Comprehensive Computational Chemistry. Elsevier, Oxford, 2024, 2: 240. https://doi.org/10.1016/B978-0-12-821978-2.00076-3.
[21] Lu T, Chen F W. Journal of Computational Chemistry, 2012, 33(5): 580.
[22] Lu T, Chen Q. Chemistry Methods, 2021, 1(5): 231.