Study of the Deformation/Interaction Model: How Interactions Increase the Reaction Barrier
The interactions (including weak interactions) between dienophiles and dienes play an important role in the Diels-Alder reaction. To elucidate the influence of these interactions on the reactivity, a popular DFT functional and a variational DFT functional corrected with dispersion terms are used to...
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| Main Authors: | , , , , , , , , |
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| Format: | Article |
| Language: | English |
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Wiley
2018-01-01
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| Series: | Journal of Chemistry |
| Online Access: | http://dx.doi.org/10.1155/2018/3106297 |
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| _version_ | 1832566589555212288 |
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| author | Zhiling Liang Houhe Liu Nianjun Su Dandan Song Yun Zhang Hong Huang Jianqi Zheng Cheng Zhong Guodong Ye |
| author_facet | Zhiling Liang Houhe Liu Nianjun Su Dandan Song Yun Zhang Hong Huang Jianqi Zheng Cheng Zhong Guodong Ye |
| author_sort | Zhiling Liang |
| collection | DOAJ |
| description | The interactions (including weak interactions) between dienophiles and dienes play an important role in the Diels-Alder reaction. To elucidate the influence of these interactions on the reactivity, a popular DFT functional and a variational DFT functional corrected with dispersion terms are used to investigate different substituent groups incorporated on the dienophiles and dienes. The bond order is used to track the trajectory of the cycloaddition reaction. The deformation/interaction model is used to obtain the interaction energy from the reactant complex to the inflection point until reaching the saddle point. The interaction energy initially increases with a decrease in the interatomic distance, reaching a maximum value, but then decreases when the dienophiles and dienes come closer. Reduced density gradient and chemical energy component analysis are used to analyse the interaction. Traditional transition state theory and variational transition state theory are used to obtain the reaction rates. The influence of tunneling on the reaction rate is also discussed. |
| format | Article |
| id | doaj-art-03407c872b4d4c2cba93e12e34c51d06 |
| institution | Kabale University |
| issn | 2090-9063 2090-9071 |
| language | English |
| publishDate | 2018-01-01 |
| publisher | Wiley |
| record_format | Article |
| series | Journal of Chemistry |
| spelling | doaj-art-03407c872b4d4c2cba93e12e34c51d062025-02-03T01:03:37ZengWileyJournal of Chemistry2090-90632090-90712018-01-01201810.1155/2018/31062973106297Study of the Deformation/Interaction Model: How Interactions Increase the Reaction BarrierZhiling Liang0Houhe Liu1Nianjun Su2Dandan Song3Yun Zhang4Hong Huang5Jianqi Zheng6Cheng Zhong7Guodong Ye8Guangdong Provincial Key Laboratory of Molecular Target & Clinical Pharmacology, School of Pharmaceutical Sciences, Guangzhou Medical University and The Fifth Affiliated Hospital of Guangzhou Medical University, Guangzhou 510700, ChinaGuangdong Provincial Key Laboratory of Molecular Target & Clinical Pharmacology, School of Pharmaceutical Sciences, Guangzhou Medical University and The Fifth Affiliated Hospital of Guangzhou Medical University, Guangzhou 510700, ChinaDepartment of Reproductive Health and Infertility, Guangdong Women and Children Hospital, Guangzhou 510010, ChinaGuangdong Provincial Key Laboratory of Molecular Target & Clinical Pharmacology, School of Pharmaceutical Sciences, Guangzhou Medical University and The Fifth Affiliated Hospital of Guangzhou Medical University, Guangzhou 510700, ChinaGuangdong Provincial Key Laboratory of Molecular Target & Clinical Pharmacology, School of Pharmaceutical Sciences, Guangzhou Medical University and The Fifth Affiliated Hospital of Guangzhou Medical University, Guangzhou 510700, ChinaGuangdong Provincial Key Laboratory of Molecular Target & Clinical Pharmacology, School of Pharmaceutical Sciences, Guangzhou Medical University and The Fifth Affiliated Hospital of Guangzhou Medical University, Guangzhou 510700, ChinaThe First Clinical School of Guangzhou Medical University, Guangzhou 510275, ChinaCollege of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, ChinaGuangdong Provincial Key Laboratory of Molecular Target & Clinical Pharmacology, School of Pharmaceutical Sciences, Guangzhou Medical University and The Fifth Affiliated Hospital of Guangzhou Medical University, Guangzhou 510700, ChinaThe interactions (including weak interactions) between dienophiles and dienes play an important role in the Diels-Alder reaction. To elucidate the influence of these interactions on the reactivity, a popular DFT functional and a variational DFT functional corrected with dispersion terms are used to investigate different substituent groups incorporated on the dienophiles and dienes. The bond order is used to track the trajectory of the cycloaddition reaction. The deformation/interaction model is used to obtain the interaction energy from the reactant complex to the inflection point until reaching the saddle point. The interaction energy initially increases with a decrease in the interatomic distance, reaching a maximum value, but then decreases when the dienophiles and dienes come closer. Reduced density gradient and chemical energy component analysis are used to analyse the interaction. Traditional transition state theory and variational transition state theory are used to obtain the reaction rates. The influence of tunneling on the reaction rate is also discussed.http://dx.doi.org/10.1155/2018/3106297 |
| spellingShingle | Zhiling Liang Houhe Liu Nianjun Su Dandan Song Yun Zhang Hong Huang Jianqi Zheng Cheng Zhong Guodong Ye Study of the Deformation/Interaction Model: How Interactions Increase the Reaction Barrier Journal of Chemistry |
| title | Study of the Deformation/Interaction Model: How Interactions Increase the Reaction Barrier |
| title_full | Study of the Deformation/Interaction Model: How Interactions Increase the Reaction Barrier |
| title_fullStr | Study of the Deformation/Interaction Model: How Interactions Increase the Reaction Barrier |
| title_full_unstemmed | Study of the Deformation/Interaction Model: How Interactions Increase the Reaction Barrier |
| title_short | Study of the Deformation/Interaction Model: How Interactions Increase the Reaction Barrier |
| title_sort | study of the deformation interaction model how interactions increase the reaction barrier |
| url | http://dx.doi.org/10.1155/2018/3106297 |
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