自由基-三重态对化学诱导动态电子极化强度的全哈密顿计算(英文)

基于考虑含E(S2Tξ-S2Tη)项的相互作用全哈密顿,利用密度矩阵运动方程,对自由基-三重态对机理的CIDEP强度进行了详细的理论计算.计算结果表明:四重态母体自由基-三重态机理(QP-RTPM)和二重态母体自由基-三重态机理(DP-RTPM)分别使稳定自由基形成发射+发射/吸收(E+E/A)和吸收+吸收/发射(A+A/E)型多重性极化,其中净E(A)极化由零场分裂相互作用产生,超精细相关E/A(A/E)极化由超精细相互作用产生.另外,零场分裂相互作用项E(S2Tξ-S2Tη),使稳定自由基的净极化减弱

Theoretical calculation on CIDEP intensity of radical-triplet pairs based on the full interaction Hamiltonian

Based on the whole zero field splitting (zfs) inte raction of triplet molecule in the interaction Hamiltonian of stable radicals and excited triplet molecules complexes, the intensity of chemical induced dynamic electron polarization (CIDEP) originated from RTPM were theoretically calculated in detail. In the calculation, the second order perturbation theory and the motion equation are used. The result of calculation indicates that the polarization pattern is hyperfine related E+E/A or A+A/E pattern, in which the net emissive or net absorptive polarization results from the zero field splitting (zfs) and the E/A or A/E polarization results from hyperfine (hf) interactions of the radical. Furthermore, the zero field splitting interaction E(S2Tξ-S2Tη) makes the net polarization decrease and the hyperfine dependent polarization increase.