Molecular properties from MCSCF‐SCEP wave functions. I. Accurate dipole moment functions of OH, OH−, and OH+
Molecular properties from MCSCF‐SCEP wave functions. I. Accurate dipole moment functions of OH, OH−, and OH+
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MCSCF-SCEP 波函数的分子特性 I. OH、OH− 和 OH+ 的精确偶极矩函数。
DOI：
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发表时间：
1983
期刊：
影响因子：
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通讯作者：
E. Reinsch
中科院分区：
文献类型：
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作者：
H. Werner;P. Rosmus;E. Reinsch
OH、OH− 和 OH+ 基态的势能和偶极矩函数是根据 MCSCF、MCSCF-SCEP 和 SCEP-CEPA 电子波函数计算得出的。研究了偶极矩相对于 MCSCF 程序中同时优化的构型数量（最多 598 个）和轨道（最多 14 个）以及 MCSCF-SCEP 波函数（最多 69 830 个构型）中的参考构型数量（最多 11 个）的稳定性。从最佳电子波函数获得的偶极矩函数比以前计算的所有偶极矩函数都更准确。对以前计算的缺陷进行了批判性分析。预计 OH− 和 OH+ 离子是比中性 OH 自由基更强的红外发射体。对于 OH、OH− 和 OH+，基本跃迁的自发发射 A10 的无旋转速率经计算分别为 12.2、137 和 263 s−1。计算出的振动基态偶极矩为 1.65、1.04、...
Potential energy and dipole moment functions for the ground states of OH, OH−, and OH+ have been calculated from MCSCF, MCSCF‐SCEP, and SCEP‐CEPA electronic wave functions. The stability of the dipole moments with respect to the number of configurations (up to 598) and orbitals (up to 14) simultaneously optimized in the MCSCF procedure and the number of reference configurations (up to 11) in the MCSCF‐SCEP wave functions (up to 69 830 configurations) has been investigated. The dipole moment functions obtained from the best electronic wave functions are more accurate than all previously calculated ones. The deficiencies of the former calculations have been critically analyzed. The OH− and OH+ ions are predicted to be stronger IR emitters than the neutral OH radical. The rotationless rates of spontaneous emission A10 for the fundamental transitions are calculated to be 12.2, 137, and 263 s−1 for OH, OH−, and OH+, respectively. The calculated dipole moments in the vibrational ground states are 1.65, 1.04, an...