液态聚乙二醇CH<sub>2</sub>剪切振动和扭转振动——拉曼光谱和密度泛函理论计算

引用本文: 韩磊, 彭丽, 蔡凌云, 郑旭明, 张富山. 液态聚乙二醇CH₂剪切振动和扭转振动——拉曼光谱和密度泛函理论计算[J]. 物理化学学报, 2017, 33(5): 1043-1050. doi: 10.3866/PKU.WHXB201702083 shu

Citation: HAN Lei, PENG Li, CAI Ling-Yun, ZHENG Xu-Ming, ZHANG Fu-Shan. CH₂ Scissor and Twist Vibrations of Liquid Polyethylene Glycol ——Raman Spectra and Density Functional Theory Calculations[J]. Acta Physico-Chimica Sinica, 2017, 33(5): 1043-1050. doi: 10.3866/PKU.WHXB201702083 shu

液态聚乙二醇CH₂剪切振动和扭转振动——拉曼光谱和密度泛函理论计算

韩磊 ^1, ,
彭丽 ^1, ,
蔡凌云 ^1, ,
郑旭明 ^1, ,
张富山 ^2,

1.
浙江理工大学化学系, 杭州 310018;
2.
恒安集团技术中心, 福建晋江 362261
基金项目:
国家自然科学基金（21473163）及国家基础研究发展规划项目（973）（2013CB834604）资助

摘要: 提出了一种新方案，以有效洞察液态中共存构象异构体对聚氧乙烯（PEO）实际振动光谱的贡献。通过定义6种－（CH₂CH₂O）－重复单元构象，构建并优化得到4种全同EO构象组合[（TGT）₁₀、（TTT）₁₀、（TTG）₁₀和（GTG）₁₀]和3种其它EO构象组合的构象异构体结构，并在PCM溶剂模型和B3LYP/6-31G（d）理论水平下，对结构进行了优化和振动频率计算。通过振动模式分析，提出描述PEO400各构象异构体的不同CH₂剪切振动和CH₂扭转振动模式的统一标准，确定了4 种CH₂CH₂－O－CH₂CH₂链段构象和相关振动模式，以及它们与振动频率大小的关系，并应用于实际拉曼光谱的指认。

关键词:

English

CH₂ Scissor and Twist Vibrations of Liquid Polyethylene Glycol ——Raman Spectra and Density Functional Theory Calculations

1.
Department of Chemistry, Zhejiang Sci-Tech University, Hangzhou 310018, P. R. China;
2.
Technology Center, Hengan Group, Jinjiang 362261, Fujian Province, P. R. China
Received Date: 28 November 2016
Revised Date: 21 January 2017
Available Online: 08 February 2017
Fund Project:
The project was supported by the National Natural Science Foundation of China (21473163) and National Basic Research Program of China (973) (2013CB834604).

Abstract: A new method is developed to effectively study the contributions of various coexisting conformations to the actual vibrational spectrum of liquid polyethylene oxide (PEO). By defining six conformations for the －(CH₂CH₂O)－ unit, four isomers from the combinations of all the same EO conformations [(TGT)₁₀, (TTT)₁₀, (TTG)₁₀, and (GTG)₁₀] and three isomers from the combinations of other EO conformations were constructed. Their optimized geometric structures and the corresponding vibrational frequencies were then computed. The unified standards that describe the different types of the CH₂ scissor and CH₂ twist vibrational modes for PEO400 are proposed through the analysis of the normal modes. The relationships between the four CH₂CH₂－OCH₂CH₂ conformations and the various CH₂ scissor and CH₂ twist vibrational modes and frequencies are determined, and the results are used to assign the practical vibrational spectra.

Key words:

1. [1]
  Miyazawa, T.; Fukushima, K.; Ideguchi, Y. J. Chem. Phys. 1962, 37, 2764. doi: 10.1063/1.1733103
2. [2]
  Yoshihara, T.; Tadokoro, H.; Murahashi, S. J. Chem. Phys. 1964, 41, 2902. doi: 10.1063/1.1726373
3. [3]
  Koenig, J. L.; Angood, A. C. J. Polym. Sci. A 1970, 8, 1787.
4. [4]
  Tadokoro, H.; Chatani, Y.; Yoshihara, T.; Tarahara, S.; Murahashi, S. Makromol. Chem. 1964, 73, 109.
5. [5]
  Matsuura, H.; Miyazawa, T. J. Polym. Sci. A 1969, 7, 1735.
6. [6]
  Takahashi, Y.; Tadokoro, H. Macromolecules 1973, 6, 673.
7. [7]
  Matsuura, H.; Miyazawa, T. Bull. Chem. Soc. Jap. 1968, 41, 1798.
8. [8]
  Yakoyama, M.; Ochi, H.; Tadokoro, H.; Price, C. Macromolecules 1972, 5, 690.
9. [9]
  Rabolt, J. F.; Johnson, K.W.; Zitter, R. N. J. Chem. Phys. 1974, 61, 504. doi: 10.1063/1.1681924
10. [10]
  Migliardo, F.; Magazù, S.; Caccamo, M. T. J. Mol. Struct. 2013, 1048, 261. doi: 10.1016/j.molstruc.2013.05.060
11. [11]
  Chaurasia, S. K.; Singh, R. K.; Chandra, S. Vibrational Spectroscopy 2013, 68, 190. doi: 10.1016/j.vibspec.2013.08.001
12. [12]
  Frech, R.; Huang, W. Macromolecules 1995, 28, 1246.
13. [13]
  Chatani, Y.; Fujii, Y.; Takayanagi, T.; Homma, A. Polymer 1990, 31, 2238.
14. [14]
  Chatani, Y.; Okamura, S. Polymer 1987, 28, 1815.
15. [15]
  Iwamoto, R.; Saito, Y.; Ishihara, H.; Tadokoro, H. J. Polym. Sci. Polym. Phys. Ed. 1968, 6, 1509.
16. [16]
  Yokoyama, M.; Ishihara, H.; Iwamoto, R.; Tadokoro, H.; Macromolecules 1969, 2, 184.
17. [17]
  Paoke, B. L.; Ratner, M. A.; Shriver, D. F. J. Phys. Chem. Solids 1981, 42, 493.
18. [18]
  Shephard, J. J.; Bremer, P. J.; McQuillan, A. J. J. Phys. Chem. B 2009, 113, 14229. doi: 10.1021/jp905149z

扫一扫看文章

计量

PDF下载量: 1
文章访问数: 369
HTML全文浏览量: 49

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

液态聚乙二醇CH₂剪切振动和扭转振动——拉曼光谱和密度泛函理论计算

English

CH₂ Scissor and Twist Vibrations of Liquid Polyethylene Glycol ——Raman Spectra and Density Functional Theory Calculations

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？

计量

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

液态聚乙二醇CH2剪切振动和扭转振动——拉曼光谱和密度泛函理论计算

English

CH2 Scissor and Twist Vibrations of Liquid Polyethylene Glycol ——Raman Spectra and Density Functional Theory Calculations

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？

计量

文章相关

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

液态聚乙二醇CH₂剪切振动和扭转振动——拉曼光谱和密度泛函理论计算

CH₂ Scissor and Twist Vibrations of Liquid Polyethylene Glycol ——Raman Spectra and Density Functional Theory Calculations

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs