{"type":"preprint","date_created":"2022-10-11T08:11:10Z","title":"On the Role of Hydrogen Bond Strength and Charge Transfer of a Diels-Alder Reaction On-Water: Semiempirical and Free Energy Calculations.","publication_status":"published","author":[{"id":"67235","first_name":"Andres","full_name":"Henao Aristizabal, Andres","last_name":"Henao Aristizabal"},{"first_name":"Yomna","last_name":"Gohar","full_name":"Gohar, Yomna"},{"last_name":"Whilhelm","full_name":"Whilhelm, René","first_name":"René"},{"first_name":"Thomas","id":"49079","last_name":"Kühne","full_name":"Kühne, Thomas"}],"status":"public","date_updated":"2022-10-11T08:11:23Z","_id":"33678","language":[{"iso":"eng"}],"year":"2022","abstract":[{"text":"<jats:p>Accelerated chemistry at the interface with water has received increasing attention. The mechanisms behind the enhanced reactivity On-Water are not yet clear. In this work we use a Langevin scheme in the spirit of second generation Car-Parrinello to accelerate the second-order density functional Tight-Binding (DFTB2) method in order to investigate the free energy of two Diels-Alder reaction On-Water: the cycloaddition between cyclopentadiene and ethyl cinnamate or thionocinnamate. The only difference between the reactants is the substitution of a carbonyl oxygen for a thiocarbonyl sulfur, making possible the distinction between them as strong and weak hydrogen-bond acceptors. We find a different mechanism for the reaction during the transition states and uncover the role of hydrogen bonds along with the reaction path. Our results suggest that acceleration of Diels-Alder reactions do not arise from an increased number of hydrogen bonds at the transition state and charge transfer plays a significant role. However, the presence of water and hydrogen-bonds is determinant for the catalysis of these reactions.</jats:p>","lang":"eng"}],"department":[{"_id":"613"}],"publisher":"American Chemical Society (ACS)","citation":{"mla":"Henao Aristizabal, Andres, et al. <i>On the Role of Hydrogen Bond Strength and Charge Transfer of a Diels-Alder Reaction On-Water: Semiempirical and Free Energy Calculations.</i> American Chemical Society (ACS), 2022.","apa":"Henao Aristizabal, A., Gohar, Y., Whilhelm, R., &#38; Kühne, T. (2022). <i>On the Role of Hydrogen Bond Strength and Charge Transfer of a Diels-Alder Reaction On-Water: Semiempirical and Free Energy Calculations.</i> American Chemical Society (ACS).","ieee":"A. Henao Aristizabal, Y. Gohar, R. Whilhelm, and T. Kühne, “On the Role of Hydrogen Bond Strength and Charge Transfer of a Diels-Alder Reaction On-Water: Semiempirical and Free Energy Calculations.” American Chemical Society (ACS), 2022.","short":"A. Henao Aristizabal, Y. Gohar, R. Whilhelm, T. Kühne, (2022).","chicago":"Henao Aristizabal, Andres, Yomna Gohar, René Whilhelm, and Thomas Kühne. “On the Role of Hydrogen Bond Strength and Charge Transfer of a Diels-Alder Reaction On-Water: Semiempirical and Free Energy Calculations.” American Chemical Society (ACS), 2022.","ama":"Henao Aristizabal A, Gohar Y, Whilhelm R, Kühne T. On the Role of Hydrogen Bond Strength and Charge Transfer of a Diels-Alder Reaction On-Water: Semiempirical and Free Energy Calculations. Published online 2022.","bibtex":"@article{Henao Aristizabal_Gohar_Whilhelm_Kühne_2022, title={On the Role of Hydrogen Bond Strength and Charge Transfer of a Diels-Alder Reaction On-Water: Semiempirical and Free Energy Calculations.}, publisher={American Chemical Society (ACS)}, author={Henao Aristizabal, Andres and Gohar, Yomna and Whilhelm, René and Kühne, Thomas}, year={2022} }"},"user_id":"71051"}