The effect of the nonplanarity of heterocyclic analogues of fluorene with the phosphorus atom on spin-orbit interactions

The transition dipole moments P00s for the transitions from the sublevels s = z, y, and x of the triplet electronic states 3A″, which are caused by intramolecular spin-orbit (SO) interactions, are calculated. The calculation is carried out for molecules of heterocyclic analogues of fluorene containing phosphorus and nitrogen (namely, the groups P-H, P-C6H5, and N-H). The influence that the planar and nonplanar models of the molecules, as well as the substituents -C6H5 and -H at the heteroatom (HA), exert on the values of (P00s)2 and on the directions of the corresponding vectors is considered. The values of the component kSO ∼ ∑s (P00s)2 of the radiative deactivation rate constant of the T1 state are calculated. It is ascertained that, in the series of molecules with HA = N, O, P, and S, both the calculated values of kso and those experimentally determined from an analysis of the intensity distribution in fine-structure phosphorescence spectra vary little, whereas the constant of the SO coupling in the heteroatom ςHA increases substantially along this series. The reason for the weak influence of ςHA on values of k so - common for both planar and nonplanar molecules - is found. ©2004 MAIK "Nauka/Interperiodica".

Authors
Gastilovich E.A.1 , Godik V.A. 2 , Korol'kova N.V.1 , Klimenko V.G.1 , Nurmukhametov R.N.1 , Serov S.A.1
Number of issue
2
Language
English
Pages
187-194
Status
Published
Volume
97
Year
2004
Organizations
  • 1 State Scientific Center, Russian Federation, Karpov Inst. of Physical Chemistry, Moscow, 105064, Russian Federation
  • 2 Russ. Univ. of Peoples' Friendship, Moscow, 113093, Russian Federation
Keywords
Carbon; Frequencies; Nitrogen; Phosphorescence; Phosphorus; Raman scattering; Rate constants; Solid solutions; Franck-Condon factors; Heteroatoms; Torsion angles; Vibronic lines; Aromatic hydrocarbons; Carbon; Frequencies; Hydrocarbons; Nitrogen; Phosphorescence; Phosphors
Date of creation
19.10.2018
Date of change
19.10.2018
Short link
https://repository.rudn.ru/en/records/article/record/3607/
Share

Other records