Theoretical study of the dipole moment function of OH(X 2Π)
- 15 June 1987
- journal article
- research article
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 86 (12), 6992-6999
- https://doi.org/10.1063/1.452347
Abstract
The convergence of the electric dipole moment function for the X 2Π state of OH is studied as a function of extensions of both the one‐particle and n‐particle basis sets. Full configuration‐interaction (FCI) energies and dipole moments in both [4s3p1d/2s1p] and [4s3p2d/2s1p] Gaussian basis sets are used for the calibration of a variety of approximate methods of including electron correlation. A CASSCF/MRSDCI treatment, which accurately reproduces the FCI potential and dipole moment function, is then performed in an extended [6s5p4d2f1g/4s3p2d] one‐particle basis set. The dipole moment is evaluated both as an expectation value and as an energy derivative. The energy derivative is found to be generally superior, especially for the coupled pair functional approaches. Our best dipole moment function gives a permanent dipole moment within 0.01 D of experiment for v=0, and within 10% of the accurate experimental value for the difference in dipole moments between v=0 and v=1. However, our theoretical value for v=2 does not lie within the experimental error bounds.Keywords
This publication has 40 references indexed in Scilit:
- Theoretical study of the electric dipole moment function of the ClO moleculeThe Journal of Chemical Physics, 1986
- Benchmark full configuration-interaction calculations on H2O, F, and F−The Journal of Chemical Physics, 1986
- Benchmark full configuration-interaction calculations on HF and NH2The Journal of Chemical Physics, 1986
- Electric dipole moment of X2Π OH and OD in several vibrational statesCanadian Journal of Physics, 1984
- Carbon, nitrogen, and oxygen abundances in BetelgeuseThe Astrophysical Journal, 1984
- The pure rotation spectrum of OH and the solar oxygen abundanceThe Astrophysical Journal, 1984
- The surface glow of the Atmosphere Explorer C and E satellitesGeophysical Research Letters, 1983
- The externally contracted CI method applied to N2International Journal of Quantum Chemistry, 1983
- Rotational analysis of hydroxyl vibration–rotation emission bands: Molecular constants for OH X2Π, 6 ≤ ν ≤ 10Canadian Journal of Physics, 1982
- Study of the ground state potential curve and dipole moment of OH by the method of optimized valence configurationsThe Journal of Chemical Physics, 1974