Mok Daniel K W, Lee Edmond P F, Chau Foo-Tim, Dyke John M
Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hung Hom, Hong Kong.
Phys Chem Chem Phys. 2008 Dec 28;10(48):7270-7. doi: 10.1039/b809863h. Epub 2008 Oct 29.
Restricted-spin coupled-cluster single-double plus perturbative triple excitation {RCCSD(T)} potential energy functions (PEFs) of the X[combining tilde]1A1 state of HfO2 and the X[combining tilde]2A1 state of HfO2- were computed, employing the quasi-relativistic effective core potential, ECP60MWB, and an associated contracted [13s6p6d4f3g2h] basis set designed for Hf, and the augmented correlation-consistent polarized valence quadruple-zeta (aug-cc-pVQZ) basis set for O. Based on the differences between the computed r0 and re geometrical parameters obtained from the PEF, and available experimentally derived r0 geometrical parameters of the X[combining tilde]1A1 state of HfO2, the experimental re geometrical parameters of the X[combining tilde]1A1 state of HfO2 were estimated as:-re(HfO)=1.7751 A and thetae(OHfO)=107.37 degrees. In addition, Franck-Condon factors for the HfO2 (X[combining tilde]1A1)+e<--HfO2- (X[combining tilde]2A1) electron detachment process, which include allowance for Duschinsky rotation and anharmonicity, were calculated using the computed RCCSD(T) PEFs, and were used to simulate the HfO2 (X[combining tilde]1A1)+e<--HfO2- (X[combining tilde]2A1) photodetachment band of HfO2-. Employing the estimated experimental re geometrical parameters of the X[combining tilde]1A1 state of HfO2 obtained in this work, the iterative Franck-Condon analysis (IFCA) procedure was carried out to optimize the geometrical parameters of the X[combining tilde]2A1 state of HfO2- until the simulated spectrum matched best with the experimental 355 nm photodetachment spectrum of W. Zheng, et. al., J. Phys. Chem. A, 1998, 102, 9129. The equilibrium geometrical parameters of X[combining tilde]2A1 state of HfO2- derived via the IFCA procedure are re(HfO)=1.823 A and thetae(OHfO)=111.5 degrees. Further calculations on low-lying triplet states of HfO2 gave adiabatic electronic energies (Te's) of, and vertical excitation energies (Tvert's) to, the ã 3B2, b[combining tilde]3B1, c[combining tilde]3A1 and d[combining tilde]3A2 states of HfO2 (from the X[combining tilde]1A1 state of HfO2), as well as electron affinities (EAs) and vertical detachment energies (VDEs) to these neutral states from the X[combining tilde]2A1 state of HfO2-.
采用准相对论有效核势ECP60MWB和为铪设计的相关收缩[13s6p6d4f3g2h]基组，以及为氧设计的增强相关一致极化价四重zeta（aug-cc-pVQZ）基组，计算了HfO₂的X̃¹A₁态和HfO₂⁻的X̃²A₁态的受限自旋耦合簇单双加微扰三重激发{RCCSD(T)}势能函数（PEF）。根据从PEF获得的计算出的r₀和rₑ几何参数与HfO₂的X̃¹A₁态的可用实验推导的r₀几何参数之间的差异，估计了HfO₂的X̃¹A₁态的实验rₑ几何参数为：rₑ(HfO)=1.7751 Å且θₑ(OHfO)=107.37°。此外，使用计算出的RCCSD(T) PEF计算了HfO₂ (X̃¹A₁)+e⇌HfO₂⁻ (X̃²A₁) 电子脱离过程的弗兰克 - 康登因子，其中包括考虑杜施金斯基旋转和非谐性，并用于模拟HfO₂⁻的HfO₂ (X̃¹A₁)+e⇌HfO₂⁻ (X̃²A₁) 光脱离带。利用在这项工作中获得的估计的HfO₂的X̃¹A₁态的实验rₑ几何参数，进行了迭代弗兰克 - 康登分析（IFCA）程序，以优化HfO₂⁻的X̃²A₁态的几何参数，直到模拟光谱与W. Zheng等人在《物理化学杂志A》1998年第102卷第9129页发表的实验355 nm光脱离光谱最佳匹配。通过IFCA程序得出的HfO₂⁻的X̃²A₁态的平衡几何参数为rₑ(HfO)=1.823 Å且θₑ(OHfO)=111.5°。对HfO₂的低激发三重态的进一步计算给出了HfO₂（从HfO₂的X̃¹A₁态）到ã³B₂、b̃³B₁、c̃³A₁和d̃³A₂态的绝热电子能量（Tₑ's）和垂直激发能量（Tvert's），以及从HfO₂⁻的X̃²A₁态到这些中性态的电子亲和能（EAs）和垂直脱离能量（VDEs）。
