Taylor Mark S, Muntean Felician, Lineberger W Carl, McCoy Anne B
JILA, Department of Chemistry and Biochemistry, University of Colorado, Boulder, Colorado 80309, USA.
J Chem Phys. 2004 Sep 22;121(12):5688-99. doi: 10.1063/1.1782191.
An ab initio investigation of the potential energy surfaces and vibrational energies and wave functions of the anion, neutral, and cation Cu(H(2)O) complexes is presented. The equilibrium geometries and harmonic frequencies of the three charge states of Cu(H(2)O) are calculated at the MP2 level of theory. CCSD(T) calculations predict a vertical electron detachment energy for the anion complex of 1.65 eV and a vertical ionization potential for the neutral complex of 6.27 eV. Potential energy surfaces are calculated for the three charge states of the copper-water complexes. These potential energy surfaces are used in variational calculations of the vibrational wave functions and energies and from these, the dissociation energies D(0) of the anion, neutral, and cation charge states of Cu(H(2)O) are predicted to be 0.39, 0.16, and 1.74 eV, respectively. In addition, the vertical excitation energies, that correspond to the 4 (2)P<--4 (2)S transition of the copper atom, and ionization potentials of the neutral Cu(H(2)O) are calculated over a range of Cu(H(2)O) configurations. In hydrogen-bonded, Cu-HOH configurations, the vertical excitation and ionization energies are blueshifted with respect to the corresponding values for atomic copper, and in Cu-OH(2) configurations where the copper atom is located near the oxygen end of water, both quantities are redshifted.
本文对阴离子、中性和阳离子Cu(H₂O)配合物的势能面、振动能及波函数进行了从头算研究。在MP2理论水平上计算了Cu(H₂O)三种电荷态的平衡几何结构和谐振频率。CCSD(T)计算预测阴离子配合物的垂直电子脱离能为1.65 eV，中性配合物的垂直电离势为6.27 eV。计算了铜-水配合物三种电荷态的势能面。这些势能面用于振动波函数和能量的变分计算，据此预测Cu(H₂O)阴离子、中性和阳离子电荷态的离解能D(0)分别为0.39、0.16和1.74 eV。此外，在一系列Cu(H₂O)构型上计算了与铜原子的4(²P)←4(²S)跃迁相对应的垂直激发能以及中性Cu(H₂O)的电离势。在氢键连接的Cu-HOH构型中，垂直激发能和电离能相对于原子铜的相应值发生蓝移，而在铜原子位于水的氧端附近的Cu-OH₂构型中，这两个量均发生红移。
