[Al2O4](-), a Benchmark Gas-Phase Class II Mixed-Valence Radical Anion for the Evaluation of Quantum-Chemical Methods.
[Al2O4](-), a Benchmark Gas-Phase Class II Mixed-Valence Radical Anion for the Evaluation of Quantum-Chemical Methods.
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[Al2O4](-)，用于评估量子化学方法的基准气相 II 类混合价自由基阴离子
DOI：
10.1021/acs.jctc.6b00594
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发表时间：
2016
影响因子：
5.5
通讯作者：
F. Bischoff
中科院分区：
文献类型：
--
作者：
M. Kaupp;A. Karton;F. Bischoff
自由基阴离子[Al2O4]−在Robin/Day分类中被认为是具有部分局域、弱耦合II类特征的小气相混合价体系的罕见例子。它在相对能量约为70kJ/mol时表现出一个带有一个末端氧自由基的低位C2v极小值和一个高位D2h极小值，并具有主要的桥式局域空穴特征。两个恒定的C2v极小值和D2h极小值由两个C2v对称的过渡态相连，这两个过渡态仅比D2h局域极小值高出约6-10kJ/mol。该系统的小尺寸和没有环境影响首次使得能够在CCSDT(Q)/CBS水平上使用W3-F12理论对II类混合价系统进行精确的从头标记能量计算。这些能量已经被用来评估基于波函数的方法[CCSD(T)，CCSD，SCS-MP2，MP2，UHF]和密度泛函，从半定域的(例如，BLYP，PBE，M06L，M11L，N12)到全局杂化(B3LYP，PBE0，BLYP35，BMK，M06，M062X，M06HF，PW6B95)和范围分离的杂化方法(CAM-B3LYP，ωB97，ωB97X-D，LC-BLYP，LC-ωPBE，M11，N12SX)，B2PLYP双杂化，以及一些局部杂化泛函。含有约35%-43%精确交换(Exx)混合燃料的全球混合动力车(如BLYP35、BMK)、几种系列混合动力车(CAM-B3LYP、ωB97X-D、ω-B97)以及本地混合动力车与基准能量学的一致性很好。相反，过低的EXX掺杂导致不正确的III类离域图像，而过大的EXX过度局域化并产生太大的能量差。这些结果支持了以前溶液中混合价体系的方法选择，以及铝硅酸盐和二氧化硅中氧缺陷位的处理。在不同计算水平下的振动气相谱直接与实验和CCSD(T)/Aug-cc-PV(T+d)Z数据进行了比较。
The radical anion [Al2O4]−has been identified as a rare example of a small gas-phase mixed-valence system with partially localized, weakly coupled class II character in the Robin/Day classification. It exhibits a low-lyingC2vminimum with one terminal oxyl radical ligand and a high-lyingD2hminimum at about 70 kJ/mol relative energy with predominantly bridge-localized-hole character. Two identicalC2vminima and theD2hminimum are connected by twoC2v-symmetrical transition states, which are only ca. 6–10 kJ/mol above theD2hlocal minimum. The small size of the system and the absence of environmental effects has for the first time enabled the computation of accurateab initiobenchmark energies, at the CCSDT(Q)/CBS level using W3-F12 theory, for a class-II mixed-valence system. These energies have been used to evaluate wave function-based methods [CCSD(T), CCSD, SCS-MP2, MP2, UHF] and density functionals ranging from semilocal (e.g., BLYP, PBE, M06L, M11L, N12) via global hybrids (B3LYP, PBE0, BLYP35, BMK, M06, M062X, M06HF, PW6B95) and range-separated hybrids (CAM-B3LYP, ωB97, ωB97X-D, LC-BLYP, LC-ωPBE, M11, N12SX), the B2PLYP double hybrid, and some local hybrid functionals. Global hybrids with about 35–43% exact-exchange (EXX) admixture (e.g., BLYP35, BMK), several range hybrids (CAM-B3LYP, ωB97X-D, ω-B97), and a local hybrid provide good to excellent agreement with benchmark energetics. In contrast, too low EXX admixture leads to an incorrect delocalized class III picture, while too large EXX overlocalizes and gives too large energy differences. These results provide support for previous method choices for mixed-valence systems in solution and for the treatment of oxyl defect sites in alumosilicates and SiO2. Vibrational gas-phase spectra at various computational levels have been compared directly to experiment and to CCSD(T)/aug-cc-pV(T+d)Z data.
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