The X̃ 1A1 → Ã 1B1 transition moment of H2O using state‐specific configuration‐interaction wave functions
The X̃ 1A1 → Ã 1B1 transition moment of H2O using state‐specific configuration‐interaction wave functions
复制标题
使用状态特定配置相互作用波函数的 H2O 的 X̃ 1A1 → à 1B1 跃迁时刻
DOI：
10.1063/1.448520
复制
发表时间：
1985
影响因子：
4.4
通讯作者：
R. Buenker
中科院分区：
文献类型：
--
作者：
G. Theodorakopoulos;I. Petsalakis;C. Nicolaides;R. Buenker
我们报道了两种计算方法对H2O X 1A1 → A 1b1跃迁振子强度的影响。一种是针对每个状态使用相关的状态特定波函数，另一种是使用具有公共基组的大的MRD-CI波函数。在第一种情况下，通过使用相应的轨道来显式地考虑非正交性。两种类型的计算都收敛到f=0.065的值。这一结果与一个实验值(f=0.060)相吻合，而与最近采用Stiltjes成像法的理论计算(f=0.021)不一致。就像以前的原子计算一样，特定状态的方法改善了激发态波函数的质量，同时显著减小了它们的尺寸。
We report the results on the oscillator strength of the H2O X 1A1 → A 1B1 transition from two types of calculations. One from using correlated state‐specific wave functions for each state and one from using large MRD‐CI wave functions with a common basis set. In the first case nonorthonormality is considered explicitly via the use of corresponding orbitals. Both types of calculation converge to a value of f=0.065. This result agrees with one experimental value (f=0.060) and disagrees with the most recent theoretical calculation which employed the Stiltjes imaging method (f=0.021). As is the case with previous atomic calculations, the state‐specific approach improves the quality of the wave functions of excited states while reducing their size considerably.