Ab Initio Study of Phosphorescence of Hetero[8]Circulenes

R. R. Valiev, G. V. Baryshnikov, V. N. Cerepanov, D. Sundholm

Research output: Contribution to journalArticle

Abstract

Quantum chemical calculations of phosphorescence lifetime are performed for the first time by ab initio CC2 and TD-DFT methods for hetero[8]circulenes bearing Si and Ge atoms. According to the results of calculations, a lower value of τphos for tetragermatetrathia[8]circulene (II) originates from two factors: almost 29 times more distorted main macrocycle II and almost four times larger spin-orbit coupling matrix element between T1 and S0 by virtue of heavier Ge atoms as compared to Si. The τphos values calculated by CC2 ideally agree with its experimental value; the difference is less than 2 and 0.3 s for tetrasilatetrathia[8]circulene (I) and tetragermatetrathia[8]circulene (II) molecules, respectively. The agreement of the lifetimes calculated by TD-DFT is only within an order of magnitude. The main intramolecular decay channel of the T1 state is internal conversion between T1 and S0 owing to simultaneous spin-orbit and nonadiabatic interaction of their wavefunctions.

Original languageEnglish
Pages (from-to)406-410
Number of pages5
JournalRussian Physics Journal
Volume62
Issue number3
DOIs
Publication statusPublished - 15 Jul 2019

Fingerprint

phosphorescence
orbits
life (durability)
internal conversion
atoms
decay
matrices
molecules
interactions

Keywords

  • circulenes
  • hetero[8]circulenes
  • oxygen
  • phosphorescence
  • photodynamic therapy
  • quantum chemistry

ASJC Scopus subject areas

  • Physics and Astronomy(all)

Cite this

Ab Initio Study of Phosphorescence of Hetero[8]Circulenes. / Valiev, R. R.; Baryshnikov, G. V.; Cerepanov, V. N.; Sundholm, D.

In: Russian Physics Journal, Vol. 62, No. 3, 15.07.2019, p. 406-410.

Research output: Contribution to journalArticle

Valiev, RR, Baryshnikov, GV, Cerepanov, VN & Sundholm, D 2019, 'Ab Initio Study of Phosphorescence of Hetero[8]Circulenes', Russian Physics Journal, vol. 62, no. 3, pp. 406-410. https://doi.org/10.1007/s11182-019-01727-7
Valiev, R. R. ; Baryshnikov, G. V. ; Cerepanov, V. N. ; Sundholm, D. / Ab Initio Study of Phosphorescence of Hetero[8]Circulenes. In: Russian Physics Journal. 2019 ; Vol. 62, No. 3. pp. 406-410.
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