Ab initio prediction of Mn2+OH2/Mn3+OH2 electron transfer reactivity at electron correlation level

Bu, Yuxiang; Song, Xinyu; Nie, Yi

doi:10.1016/s0166-1280(00)00346-8

Cited by 3 publications

(1 citation statement)

References 32 publications

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“…The golden rule is an excellent one. It has been used successfully in dealing with a number of systems, such as the ET reaction of O 2 /O

_{−}^{2}

, M 2+ OH 2 /M 3+ OH 2 (M = V, C r , and Mn) and the hydrogen transfer tunneling reaction 5, 42–47. The ET rate is expressed with a particular simple form according to the golden rule, where R a – b denotes the definite contact distance of the reaction species, H if is the coupling interaction between the initial | i 〉 and final states | f 〉, with an energy difference E f .…”

Section: Theoretical Schemesmentioning

confidence: 99%

Theoretical prediction of the contact distance dependence of the electron transfer reactivity of the ClO/ClO⁻ coupling system

Yan¹,

Bu²,

Sun³

2004

Int J of Quantum Chemistry

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ABSTRACT:On the basis of the structures and properties of the ClO/ClO Ϫ system obtained at the density functional theory (DFT) (UB3LYP) level, employing the 6-311ϩG(3df ) standard basis set, the electron transfer reactivity of this system is investigated. The results indicate that there are five possible stable coupling complexes that correspond to the generous minima on the global potential energy surfaces (PES). The most stable coupling complex is planar EC4, in which there is a OOO linkage with two trans-Cl atoms. Their stabilization energies are calculated to be 20.57 (EC1: C 1 ), 20.54 (EC2: C 2 , 2 B), 20.69 (EC3: C 1 ), 20.70 (EC4: C s , 2 AЈ), and 20.69 (EC.5: C 2h , 2 B u ) kcal/ mol at the B3LYP/6-311ϩG(3df ) level; with the correction of the basis set superposition error (BSSE), the stability order of these encounter complexes is EC4 Ͼ EC.5 Ͼ EC3 Ͼ EC1 Ͼ EC2. Based on the five encounter complexes, five coupling modes are designed for the study of the electron transfer reactivity of this system. The dissociation energy curves at the activated states and the corresponding activation energies of these five coupling modes are obtained and are compared at the B3LYP/6-311ϩG(3df ) and MP2/ 6-311ϩG* levels. The inapplicability of DFT methods has also been discussed in this article in predicting the energy curves, especially with a long contact distance, in which DFT methods give the abnormal behavior for the dissociations of the complexes caused by the "inverse symmetry breaking" problem. On the basis of the golden rule of the time-dependent perturbation theory, the electron transfer reactivity and the contact distance dependence of the various electron transfer kinetics parameters (e.g., activation energy, coupling matrix element) have been analyzed at the UMP2(full)/6-311ϩG* level. The electron transfer can take place over a range of contact distances, but the most effective coupling distance corresponds to only a small range. The coupling orientation analyses also indicate that the most favorable coupling mode to the electron transfer does not always correspond to the most stable encounter complex mechanism. Some highly energetic coupling modes are more favorable for the electron transfer.

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“…The golden rule is an excellent one. It has been used successfully in dealing with a number of systems, such as the ET reaction of O 2 /O

_{−}^{2}

Section: Theoretical Schemesmentioning

confidence: 99%

Theoretical prediction of the contact distance dependence of the electron transfer reactivity of the ClO/ClO⁻ coupling system

Yan¹,

Bu²,

Sun³

2004

Int J of Quantum Chemistry

Self Cite

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Theoretical studies on structural properties and electron transfer reactivity of the C4H4O/C4H4O+ furan coupling pair

Yan

Sun

2004

Journal of Molecular Structure: THEOCHEM

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Theoretical studies on the contact distance dependence of the electron transfer reactivity of the ClO/ClO+ coupling system

Yan

Sun

2003

New J. Chem.

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Ab initio prediction of Mn2+OH2/Mn3+OH2 electron transfer reactivity at electron correlation level

Cited by 3 publications

References 32 publications

Theoretical prediction of the contact distance dependence of the electron transfer reactivity of the ClO/ClO⁻ coupling system

Theoretical prediction of the contact distance dependence of the electron transfer reactivity of the ClO/ClO⁻ coupling system

Theoretical studies on structural properties and electron transfer reactivity of the C4H4O/C4H4O+ furan coupling pair

Theoretical studies on the contact distance dependence of the electron transfer reactivity of the ClO/ClO+ coupling system

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Ab initio prediction of Mn2+OH2/Mn3+OH2 electron transfer reactivity at electron correlation level

Cited by 3 publications

References 32 publications

Theoretical prediction of the contact distance dependence of the electron transfer reactivity of the ClO/ClO− coupling system

Theoretical prediction of the contact distance dependence of the electron transfer reactivity of the ClO/ClO− coupling system

Theoretical studies on structural properties and electron transfer reactivity of the C4H4O/C4H4O+ furan coupling pair

Theoretical studies on the contact distance dependence of the electron transfer reactivity of the ClO/ClO+ coupling system

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Theoretical prediction of the contact distance dependence of the electron transfer reactivity of the ClO/ClO⁻ coupling system

Theoretical prediction of the contact distance dependence of the electron transfer reactivity of the ClO/ClO⁻ coupling system