Premium
Energy landscape study of water splitting and H 2 evolution at a ruthenium( II ) pincer complex
Author(s) -
Yoshida Yuichiro,
Yokoi Hayato,
Sato Hirofumi
Publication year - 2020
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.26385
Subject(s) - pincer movement , ruthenium , energy landscape , maxima and minima , potential energy surface , density functional theory , water splitting , transition state , hypersurface , chemistry , computational chemistry , molecular dynamics , chemical physics , catalysis , molecule , mathematics , mathematical analysis , biochemistry , organic chemistry , photocatalysis
Abstract A bird's‐eye view of the water splitting and H 2 generation at a ruthenium(II) pincer complex is presented. Using a combination of density functional theory and efficient algorithms for exploration of potential energy hypersurface (PES), a total of 197 local minima and 186 transition states are identified, and a new mechanism for water splitting and H 2 evolution via hydroxycarbonyl intermediates is presented. Furthermore, a global feature of the reaction PES, so‐called potential energy landscape, is discussed on analyzing the obtained structures. As a result, the landscape is characterized by hierarchical structure, namely, PES consists of many “superbasins (SBs)” that are separated by relatively high energy barriers corresponding to bond breaking around Ru(II) center. Each SB involves a set of conformational isomers that can be interchanged with each other through relatively small barriers. To the best of our best knowledge, this is the first report on the quantum chemical computation of the hierarchical structure of PES for a realistic, catalytic reaction system.