Journal of Physical Chemistry A, Vol.101, No.21, 3848-3854, 1997
On the Manifestation of S-T-Transitions in Weak Magnetic-Fields - CIDNP for Radical Pairs with Large Hfi Constants
The CIDNP effects observed in photolytic reactions of (2,4,6-trimethylbenzoyl)diphenylphosphine oxide (TMBDPO) and benzoylphosphonic acid dimethyl ester (BDMP) in organic solvents of different viscosities are determined by S-T- transitions that occur in the region of energy levels crossing. An analytical expression is proposed for calculation of the CIDNP effects at weak magnetic fields, which takes into account the S-T- transitions due to energy levels crossing. The experimental data are compared to the results obtained by the numerical solution of the stochastic Liouville equation (SLE) for a microreactor model. The parameters that affect the efficiency of the S-T- transitions are discussed.
Keywords:LASER FLASH-PHOTOLYSIS;STIMULATED NUCLEAR-POLARIZATION;ELECTRON-SPIN POLARIZATION;ACYLPHOSPHINE OXIDES;2;4;6-TRIMETHYLBENZOYLDIPHENYLPHOSPHINE OXIDE;EXCHANGE;PHOTODECOMPOSITION;APPROXIMATION;DEPENDENCE;RESONANCE