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 language | English |
|---|---|
| Pages (from-to) | 406-410 |
| Number of pages | 5 |
| Journal | Russian Physics Journal |
| Volume | 62 |
| Issue number | 3 |
| DOIs | |
| Publication status | Published - 15 Jul 2019 |
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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 journal › Article
}
TY - JOUR
T1 - Ab Initio Study of Phosphorescence of Hetero[8]Circulenes
AU - Valiev, R. R.
AU - Baryshnikov, G. V.
AU - Cerepanov, V. N.
AU - Sundholm, D.
PY - 2019/7/15
Y1 - 2019/7/15
N2 - 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.
AB - 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.
KW - circulenes
KW - hetero[8]circulenes
KW - oxygen
KW - phosphorescence
KW - photodynamic therapy
KW - quantum chemistry
UR - http://www.scopus.com/inward/record.url?scp=85068888247&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85068888247&partnerID=8YFLogxK
U2 - 10.1007/s11182-019-01727-7
DO - 10.1007/s11182-019-01727-7
M3 - Article
AN - SCOPUS:85068888247
VL - 62
SP - 406
EP - 410
JO - Russian Physics Journal
JF - Russian Physics Journal
SN - 1064-8887
IS - 3
ER -