Fatigue and fatigue resistance in S1 excited state diarylethenes in electric fields. Issue 6 (9th November 2020)

• Record Type: Journal Article
• Authors: Nie, Xing; Yang, Yong; Xu, Tianlv; Kirk, Steven R.; Jenkins, Samantha
• Is Part Of: International journal of quantum chemistry. Volume 121:Issue 6(2021)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2020-11-09
• Subjects: diarylethenes -- electric‐field -- excited state -- fatigue -- next generation QTAIM; Quantum chemistry -- Periodicals; 541.28
• DOI: 10.1002/qua.26527
• Languages: English
• ISSNs: 0020-7608

Abstract

Abstract: The effect of a directional electric‐field on the bonding of the undoped and sulfur doped diarylethene (DTE) switch molecule is investigated using next generation QTAIM (NG‐QTAIM). We introduce chemical bonding concepts in the form of the least and most preferred directions of charge density accumulation relative to a bond‐path, namely the precessions K and K ′ that are demonstrated to be much more responsive to the electric‐field than the Laplacian ∇ 2 ρ (r b ). A concept of bond fatigue is presented in terms of the tendency for a bond‐path to rupture that provides directional versions of familiar bonding QTAIM concepts. Examples of fatigue resistance and fatigue are included where the applied electric‐field reduces and increases the tendency toward bond‐path rupture respectively. A brief discussion is undertaken of applications of the precessions K and K ′ including switches, ring opening reactions and molecular rotary motors in the presence of fields that cause a redistribution of ρ (r ). Abstract : Left : The C6–C12 BCP bond‐path { q, q ′} path‐packet precession K ′ for the undoped DTE. Right : Corresponding molecular graph with directions of bond critical point ( BCP ) shifts and { p, p ′} and { q, q ′} path‐packets, the fatigue bond is indicated by the black arrow. Left : The C6–S27 BCP bond‐path { q, q ′} path‐packet precession K ′ for the sulphur doped DTE. Right : Corresponding molecular graph with BCP shifts and { p, p ′} and { q, q ′} path‐packets, the fatigue bond is indicated by the yellow arrow.