The Cu2O2 torture track for a real‐life system: [Cu2(btmgp)2O2]2+ oxo and peroxo species in density functional calculations†
The Cu2O2 torture track for a real‐life system: [Cu2(btmgp)2O2]2+ oxo and peroxo species in density functional calculations†
复制标题
真实系统的 Cu2O2 折磨轨迹：密度泛函计算中的 [Cu2(btmgp)2O2]2 氧和过氧物种â
DOI：
10.1002/jcc.23983
复制
发表时间：
2015
影响因子：
3
通讯作者：
W. G. Schmidt
中科院分区：
文献类型：
--
作者：
M. Rohrmüller;A. Hoffmann;C. Thierfelder;S. Herres-Pawlis;W. G. Schmidt
用密度泛函理论计算了[Cu2(Btmgp)2(μ-O)2]2+(OxO)和[Cu2(Btmgp)2(μ-η2：η2-O2)]2+(过氧基)的平衡几何构型、振动模式、电离能、电子亲和势和光学响应。综合基准测试表明，对于DFT来说，氧代过氧基能学的描述仍然是一条折磨人的轨道，但发现分子几何相对于交换关联泛函和基组的变化是相对稳健的。纯泛函倾向于实验中发现的氧核，而混合泛函则将偏向偏向过氧核。采用破缺对称性(BS)方法对自旋自由度进行松弛，进一步稳定了过氧核。相反，分散效应倾向于氧代构型。三重Zeta基组被发现代表了数值精度和计算工作量之间的合理折衷。特别注意了氧和过氧基之间的电子结构、光学跃迁和激发态能量沿跃迁路径的改变。激发态势能面计算表明，两个三重态参与了稳定BS溶液的跃迁。电荷分解和自然跃迁轨道分析被用于获得分子轨道相互作用的微观洞察。在这里，强调了π-对稳定Cu2O2核心的关键作用。©2015 Wiley期刊，Inc.
Density functional theory (DFT) calculations of the equilibrium geometry, vibrational modes, ionization energies, electron affinities, and optical response of [Cu2(btmgp)2(μ‐O)2]2+(oxo) and [Cu2(btmgp)2(μ‐η2:η2‐O2)]2+(peroxo) are presented. Comprehensive benchmarking shows that the description of the oxo–peroxo energetics is still a torture track for DFT, but finds the molecular geometry to be comparatively robust with respect to changes in the exchange‐correlation functionals and basis sets. Pure functionals favor the oxo core found experimentally, whereas hybrid functionals shift the bias toward the peroxo core. Further stabilization of peroxo core results from relaxing the spin degrees of freedom using the broken‐symmetry (BS) approach. Dispersion effects, conversely, tend to favor the oxo configuration. Triple‐zeta basis sets are found to represent a sensible compromise between numerical accuracy and computational effort. Particular attention is paid to the modification of the electronic structure, optical transitions, and excited‐state energies along the transition path between the oxo and peroxo species. The excited‐state potential energy surface calculations indicate that two triplet states are involved in the transition that stabilize the BS solution. Charge decomposition and natural transition orbital analyses are used for obtaining microscopic insight into the molecular orbital interactions. Here, the crucial role of guanidine π‐interactions is highlighted for the stabilization of the Cu2O2core. © 2015 Wiley Periodicals, Inc.
登录
查看更多内容
具有乙烯桥联双(咪唑啉-2-亚胺)配体的铜(I)配合物的合成和反应性。
DOI：
10.1039/b715590e
发表时间：
2008
期刊：
Dalton transactions (Cambridge, England : 2003)
影响因子：
--
作者：
Petrovic,Dejan;Hill,LyndalMR;Jones,PeterG;Tolman,WilliamB;Tamm,Matthias
通讯作者：
Tamm,Matthias
由与 O2 键合的二铜结构中的羧化基团支持的舞蹈多重态
影响因子：
1.7
作者：
A. Poater;L. Cavallo
通讯作者：
L. Cavallo
深入了解色散校正对胍喹啉铜 (I) 络合物理论处理的影响
影响因子：
3
作者：
A. Hoffmann;R. Grunzke;S. Herres-Pawlis
通讯作者：
S. Herres-Pawlis
影响因子：
3
作者：
Neese, Frank
通讯作者：
Neese, Frank
Cu(III)2(mu-O)2 物种中的酪氨酸酶样反应性。
影响因子：
--
作者：
A. Company;S. Palavicini;I. Garcia;R. Mas‐Ballesté;L. Que;E. Rybak;L. Casella;X. Ribas;M. Costas
通讯作者：
M. Costas