We used density functional calculations to investigate the electronic origins of the magnetic properties of the high-spin ferric enzyme-substrate complex protocatechuate 3,4-dioxygenase(3,4-PCD).The calculated g-tenso...We used density functional calculations to investigate the electronic origins of the magnetic properties of the high-spin ferric enzyme-substrate complex protocatechuate 3,4-dioxygenase(3,4-PCD).The calculated g-tensors show that ligand-to-metal charge transfer transitions are from the protocatechuate(PCA) and Tyr408 orbitals to the Fe d orbitals,which lead to x-and y-polarized transitions.These polarized transitions require a spin-orbit coupling(SOC) matrix element in the z-direction,Lz(z=z'),resulting in a g z value of 2.0158,significantly deviating from 2.0023.A large zero-field splitting parameter value of+1.147cm-1 is due to △S =-1 spin-orbit mixing with the quartet states for the sextet ground state,accounting for around 73% of the SOC contribution.The SOC matrix elements indicate that the high-spin d 5 system Fe(Ⅲ),3,4-PCD-PCA is a weak spin-crossover compound with an SOC of 31.56 cm-1.展开更多
基金supported by the Science and Technology Development Program of Hangzhou,China (20091133B09)Zhejiang Provincial Medicine & Health Research Fund,China (2009A158)Zhejiang Provincial Public Welfare Application Project of China (2010C33132)~~
基金supported by the Key R&D Program of Zhejiang Province,China(2021C01002)the National Natural Science Foundation of China(11874320,12034017,11874137,and 11974306)+1 种基金the National Key R&D Program of China(2017YFA0303100)Zhejiang Provincial Natural Science Foundation of China(R22A0410240).
基金supported by the "QingLan" Talent Engineering Fundsthrough Tian Shui Normal Universitythe Key Project of the Chinese Ministry of Education (211189)
文摘We used density functional calculations to investigate the electronic origins of the magnetic properties of the high-spin ferric enzyme-substrate complex protocatechuate 3,4-dioxygenase(3,4-PCD).The calculated g-tensors show that ligand-to-metal charge transfer transitions are from the protocatechuate(PCA) and Tyr408 orbitals to the Fe d orbitals,which lead to x-and y-polarized transitions.These polarized transitions require a spin-orbit coupling(SOC) matrix element in the z-direction,Lz(z=z'),resulting in a g z value of 2.0158,significantly deviating from 2.0023.A large zero-field splitting parameter value of+1.147cm-1 is due to △S =-1 spin-orbit mixing with the quartet states for the sextet ground state,accounting for around 73% of the SOC contribution.The SOC matrix elements indicate that the high-spin d 5 system Fe(Ⅲ),3,4-PCD-PCA is a weak spin-crossover compound with an SOC of 31.56 cm-1.
