1H and 13C chemically induced dynamic nuclear polarization (CIDNP) and time-resolved stimulated nuclear polarization (SNP) have been applied to the investigation of spin and molecular dynamics in biradicals, generated in the photolysis of 2,2,12,12-tetramethylcyclododecanone, at low magnetic field in the temperature range from 200 to 360 K. This reaction involves two consecutive biradical stages, the primary acyl-alkyl and the secondary bis-alkyl biradical, with different reaction products. Characteristic differences in the CIDNP field dependencies and SNP decay times for nuclei of different reaction products are seen at high temperatures. Upon cooling, the emission maximum position shifts to low field and the width of the 1H CIDNP field dependencies of the acyl-alkyl biradical products decreases. Below 243 K these effects reverse direction, furthermore, a significant slowing down of the SNP decay is observed. Calculations of the 1H and 13C CIDNP field dependencies and the SNP kinetics for the primary biradical have been performed based on the numerical solution of the stochastic Liouville equation for the biradical spin density matrix. They use a model of restricted diffusion for the description of the molecular dynamics and take into account the distance dependence of the exchange interaction. Good quantitative agreement between the calculations and experimental data is found for the whole temperature range when using the appropriate dependence of some of the parameters on temperature. In particular, it was necessary for the quantitative simulation in the low temperature range to introduce a temperature dependence of the biradical reactivity. The model calculations qualitatively confirm that the low-temperature broadening of the CIDNP field dependencies, and the increase of the SNP decay time are caused by the slowing down of the molecular mobility and the decreasing of reactivity. For the products of the secondary biradical, a qualitative interpretation is given showing that in comparison with the products of the primary biradical spin-orbit interaction is of less importance for the biradical spin dynamics, that the influence of the molecular mobility under the temperature variation is more pronounced, that the lifetime is longer, and that the nuclear polarization is more efficiently formed.
Original language | English |
---|---|
Pages (from-to) | 980-988 |
Number of pages | 9 |
Journal | Journal of Physical Chemistry A |
Volume | 103 |
Issue number | 8 |
DOIs | |
State | Published - 1 Jan 1999 |
Externally published | Yes |
ID: 48946269