Citation: Ya'ni Wang, Xue-Peng Zhang. Investigations on Allyl Cation Rotational Isomerism: A Computational Experiment Design[J]. University Chemistry, ;2023, 38(2): 197-206. doi: 10.3866/PKU.DXHX202205027 shu

Investigations on Allyl Cation Rotational Isomerism: A Computational Experiment Design

Ya'ni Wang ,
Xue-Peng Zhang ^,

School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an 710119, China

Corresponding author: Xue-Peng Zhang, zhangxp@snnu.edu.cn
Received Date: 8 May 2022

In this study, a computational chemistry exploration experiment for senior undergraduate or beginning graduate students is designed. The rotational isomerization reaction of an allyl cation is investigated using density functional theory (DFT) calculations. The theoretical experiment involves molecular geometry optimization, transition state location, and establishment of intrinsic reaction coordinates (IRCs). This design can help students understand the basic concepts and operations of computational chemistry. Furthermore, the concepts of molecular microstructures and the notion of “old bonds are about to break and new bonds are about to form” in the transition state theory are discussed. This experiment will also aid the understanding of the differences between reaction thermodynamics and kinetics through the construction of potential energy surfaces. Further investigations of charge population analysis and frontier orbital analysis will aid the understanding of electronic structures of molecules as well as the concept of reaction reactive sites.
- Allyl cation,
- Rotational isomerism,
- Density functional theory,
- Potential energy surface,
- Experimental design
1. [1]
2. [2]
3. [3]
4. [4]
5. [5]
6. [6]
7. [7]
8. [8]
9. [9]
10. [10]
11. [11]
12. [12]
13. [13]
  Epstein, S. T. J. Chem. Phys. 1966, 44, 836.
14. [14]
  Roothaan, C. C. J. Rev. Mod. Phys. 1951, 23, 69.
15. [15]
  Møller, C.; Plesset, M. S. Phys. Rev. 1934, 46, 618.
16. [16]
  Bartlett, R. J.; Purvis, G. D. Int. J. Quantum Inf. 1978, 14, 561.
17. [17]
  Pople, J. A.; Seeger, R.; Krishnan, R. Int. J. Quantum Inf. 1977, 12, 149.
18. [18]
  Krishnan, R.; Schlegel, H. B.; Pople, J. A. J. Chem. Phys. 1980, 72, 4654.
19. [19]
  Raghavachari, K.; Pople, J. A. Int. J. Quantum Inf. 1981, 20, 1067.
20. [20]
  Stewart, J. J. P. J. Mol. Model. 2007, 13, 1173.
21. [21]
  Hohenberg, P.; Kohn, W. Phys. Rev. 1964, 136, B864.
22. [22]
  Kohn, W.; Sham, L. J. Phys. Rev. 1965, 140, A1133.
23. [23]
  Calais, J.-L. Int. J. Quantum Inf. 1993, 47, 101.
24. [24]
  Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F.; Frisch, M. J. J. Phys. Chem. C 1994, 98, 11623.
25. [25]
  Neese, F. WIREs Comput. Mol. Sci. 2018, 8, e1327.
26. [26]
  Schmidt, M. W.; Baldridge, K. K.; Boatz, J. A.; Elbert, S. T.; Gordon, M. S.; Jensen, J. H.; Koseki, S.; Matsunaga, N.; Nguyen, K. A.; Su, S.; et al. J. Comput. Chem. 1993, 14, 1347.
27. [27]
  Aidas, K.; Angeli, C.; Bak, K. L.; Bakken, V.; Bast, R.; Boman, L.; Christiansen, O.; Cimiraglia, R.; Coriani, S.; Dahle, P.; et al. WIREs Comput. Mol. Sci. 2014, 4, 269.
28. [28]
  Nayak, N. Y.; Nayak, S.; Nadaf, Y. F.; Shetty, S. N.; Gaonkar L. S. Lett. Org. Chem. 2020, 17, 491.
29. [29]
  Tracy, J. S.; Kalnmals, C. A.; Toste F. D. Isr. J. Chem. 2021, 61, 340.
30. [30]
  Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Petersson, G. A.; Nakatsuji, H.; et al. Gaussian 09, Revision C.01; Gaussian, Inc.:Wallingford, CT, USA, 2010.
31. [31]
32. [32]
  Mulliken, R. S. J. Chem. Phys. 1955, 23, 1833.
33. [33]
  Mulliken, R. S. J. Chem. Phys. 1955, 23, 1841.
34. [34]
  Mulliken, R. S. J. Chem. Phys. 1955, 23, 2338.
35. [35]
  Reed, A. E.; Weinstock, R. B.; Weinhold, F. J. Chem. Phys. 1985, 83, 735.
36. [36]
  Singh, U. C.; Kollman, P. A. J. Comput. Chem. 1984, 5, 129.
37. [37]
1. [1]
  Yuan Chun , Lijun Yang , Jinyue Yang , Wei Gao . Ideological and Political Design of BZ Oscillatory Reaction Experiment. University Chemistry, 2024, 39(2): 72-76. doi: 10.3866/PKU.DXHX202308072
2. [2]
  Kaifu Zhang , Shan Gao , Bin Yang . Application of Theoretical Calculation with Fun Practice in Raman Spectroscopy Experimental Teaching. University Chemistry, 2025, 40(3): 62-67. doi: 10.12461/PKU.DXHX202404045
3. [3]
  Weina Wang , Lixia Feng , Fengyi Liu , Wenliang Wang . Computational Chemistry Experiments in Facilitating the Study of Organic Reaction Mechanism: A Case Study of Electrophilic Addition of HCl to Asymmetric Alkenes. University Chemistry, 2025, 40(3): 206-214. doi: 10.12461/PKU.DXHX202407022
4. [4]
  Hao XU , Ruopeng LI , Peixia YANG , Anmin LIU , Jie BAI . Regulation mechanism of halogen axial coordination atoms on the oxygen reduction activity of Fe-N₄ site: A density functional theory study. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 695-701. doi: 10.11862/CJIC.20240302
5. [5]
  Lijuan Liu , Xionglei Wang . Preparation of Hydrogels from Waste Thermosetting Unsaturated Polyester Resin by Controllable Catalytic Degradation: A Comprehensive Chemical Experiment. University Chemistry, 2024, 39(11): 313-318. doi: 10.12461/PKU.DXHX202403060
6. [6]
  Yuai Duan , Xuanyu Gan , Yao Fu , Yingjie Cao , Hongliang Han , Zhanfang Ma . Application and Innovative Design of Digital Technology in the Preparation Experiment of Cis(Trans)-Diglycine Copper Complexes. University Chemistry, 2026, 41(1): 373-381. doi: 10.12461/PKU.DXHX202504048
7. [7]
  Xiaochen Zhang , Fei Yu , Jie Ma . Cutting-Edge Applications of Multi-Angle Numerical Simulations for Capacitive Deionization. Acta Physico-Chimica Sinica, 2024, 40(11): 2311026-0. doi: 10.3866/PKU.WHXB202311026
8. [8]
  Wei Sun , Yongjing Wang , Kun Xiang , Saishuai Bai , Haitao Wang , Jing Zou , Arramel , Jizhou Jiang . CoP Decorated on Ti₃C₂T_x MXene Nanocomposites as Robust Electrocatalyst for Hydrogen Evolution Reaction. Acta Physico-Chimica Sinica, 2024, 40(8): 2308015-0. doi: 10.3866/PKU.WHXB202308015
9. [9]
  Haiyu Nie , Chenhui Zhang , Fengpei Du . Ideological and Political Design for the Preparation, Characterization and Particle Size Control Experiment of Nanoemulsion. University Chemistry, 2024, 39(2): 41-46. doi: 10.3866/PKU.DXHX202306055
10. [10]
  Kun Li , Na Gao , Shuangyan Huan , Yuzhi Wang . Design of Ideological and Political Education for the Experiment of Detecting Cadmium with Anodic Stripping Voltammetry. University Chemistry, 2024, 39(2): 155-161. doi: 10.3866/PKU.DXHX202307068
11. [11]
  Shuyong Zhang , Shu'e Song . Ideological and Political Case Design of Experiment of Corrosion and Protection Linking with National Major Projects. University Chemistry, 2024, 39(2): 57-60. doi: 10.3866/PKU.DXHX202304078
12. [12]
  Lijun Dong , Pengcheng Du , Guangnong Lu , Wei Wang . Exploration and Practice of Independent Design Experiments in Inorganic and Analytical Chemistry: A Case Study of “Preparation and Composition Analysis of Tetraammine Copper(II) Sulfate”. University Chemistry, 2024, 39(4): 361-366. doi: 10.3866/PKU.DXHX202310041
13. [13]
  Jie ZHAO , Sen LIU , Qikang YIN , Xiaoqing LU , Zhaojie WANG . Theoretical calculation of selective adsorption and separation of CO₂ by alkali metal modified naphthalene/naphthalenediyne. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 515-522. doi: 10.11862/CJIC.20230385
14. [14]
  Jie ZHAO , Huili ZHANG , Xiaoqing LU , Zhaojie WANG . Theoretical calculations of CO₂ capture and separation by functional groups modified 2D covalent organic framework. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 275-283. doi: 10.11862/CJIC.20240213
15. [15]
  Cailin Song , Wenqi Liu , Qingming Lu , Bin Zhang , Xiaowen Xu . Determination of Iron/Zinc/Copper/Manganese in Aloe vera and Ganoderma lucidum Using Flame Atomic Absorption Spectrometry. University Chemistry, 2026, 41(4): 356-362. doi: 10.12461/PKU.DXHX202505098
16. [16]
  Tongqi Ye , Yanqing Wang , Qi Wang , Huaiping Cong , Xianghua Kong , Yuewen Ye . Reform of Classical Thermodynamics Curriculum from the Perspective of Computational Chemistry. University Chemistry, 2025, 40(7): 387-392. doi: 10.12461/PKU.DXHX202409128
17. [17]
  Xinwan Zhao , Yue Cao , Minjun Lei , Zhiliang Jin , Tsubaki Noritatsu . Constructing S-scheme heterojunctions by integrating covalent organic frameworks with transition metal sulfides for efficient noble-metal-free photocatalytic hydrogen evolution. Acta Physico-Chimica Sinica, 2025, 41(12): 100152-0. doi: 10.1016/j.actphy.2025.100152
18. [18]
  Chenxu Gong , Weizhen Wang , Ruiying Zhang , Wenfeng Wang , Yuanming Li , Yaofeng Yuan , Keyin Ye . Computational Chemistry-Assisted Organic Structure Analysis (CCAOSA): A Case Study of Propeller-Shaped Hexabenzotriphenylene. University Chemistry, 2026, 41(4): 438-446. doi: 10.12461/PKU.DXHX202503076
19. [19]
  Shuangshuang Mao , Juhua Luo , Bingjie Han , Jiahuan Shi , Yujia Gu . Covalent organic framework-derived Fe₃C/NC/TiO₂ heterostructures for high-performance electromagnetic wave absorption. Acta Physico-Chimica Sinica, 2026, 42(7): 100290-. doi: 10.1016/j.actphy.2026.100290
20. [20]
  Meifeng Zhu , Jin Cheng , Kai Huang , Cheng Lian , Shouhong Xu , Honglai Liu . Classical Density Functional Theory for Understanding Electrochemical Interface. University Chemistry, 2025, 40(3): 148-152. doi: 10.12461/PKU.DXHX202405166

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(1905)
HTML views(254)

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