The double proton transfer (PT) reaction has been investigated in the [2,2'-bipyridyl]-3-3'-diol, a complex molecule where the proton movements is coupled to significant rearrangement of the electronic structure. Moreover, the reaction could be con-certed, that is the two protons are exchanged simultaneously, or stepwise, where the two protons are transferred sequentially. To this end, a static exploration of the potential energy surface (PES) was carried together with the analysis of the free-energy surface (FES), both surfaces being evaluated at density functional theory level and different exchange-correlation functionals. While the concerted mechanism has been clearly discharged, the characteristics of the stepwise PT significantly depends on the chosen functionals, some suggesting a clear stepwise mechanism character-ized by a stable reaction intermediates and two transitions states, whereas other approaches propend for a asynchronous PT, with a single TS. These features appear on both PES and FES, albeit some differences appears due to their different nature.
Concerted versus stepwise proton transfer reactions in the [2, 2′‐bipyridyl]‐3‐3′‐diol molecule: A static and dynamic ab‐initio investigation / Briccolani‐Bandini, Lorenzo; Brémond, Eric; Pagliai, Marco; Cardini, Gianni; Ciofini, Ilaria; Adamo, Carlo. - In: JOURNAL OF COMPUTATIONAL CHEMISTRY. - ISSN 0192-8651. - STAMPA. - 44:(2023), pp. 2308-2318. [10.1002/jcc.27198]
Concerted versus stepwise proton transfer reactions in the [2, 2′‐bipyridyl]‐3‐3′‐diol molecule: A static and dynamic ab‐initio investigation
Briccolani‐Bandini, Lorenzo;Pagliai, Marco;Cardini, Gianni;
2023
Abstract
The double proton transfer (PT) reaction has been investigated in the [2,2'-bipyridyl]-3-3'-diol, a complex molecule where the proton movements is coupled to significant rearrangement of the electronic structure. Moreover, the reaction could be con-certed, that is the two protons are exchanged simultaneously, or stepwise, where the two protons are transferred sequentially. To this end, a static exploration of the potential energy surface (PES) was carried together with the analysis of the free-energy surface (FES), both surfaces being evaluated at density functional theory level and different exchange-correlation functionals. While the concerted mechanism has been clearly discharged, the characteristics of the stepwise PT significantly depends on the chosen functionals, some suggesting a clear stepwise mechanism character-ized by a stable reaction intermediates and two transitions states, whereas other approaches propend for a asynchronous PT, with a single TS. These features appear on both PES and FES, albeit some differences appears due to their different nature.File | Dimensione | Formato | |
---|---|---|---|
164105_1_online.pdf
Accesso chiuso
Tipologia:
Pdf editoriale (Version of record)
Licenza:
Tutti i diritti riservati
Dimensione
3.56 MB
Formato
Adobe PDF
|
3.56 MB | Adobe PDF | Richiedi una copia |
I documenti in FLORE sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.