Accurate {ital ab initio} near-equilibrium potential energy and dipole moment functions of the Xthinsp{sup 2}B{sub 1} and first excited {sup 2}A{sub 2} electronic states of OClO and OBrO

Journal Article · Sun Nov 01 04:00:00 EST 1998 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.477558· OSTI ID:664669

Peterson, K A ^[1]

---

1. Department of Chemistry, Washington State University, 2710 University Drive, Richland, Washington 99352 (United States)

Using highly correlated multireference configuration interaction wave functions with large correlation consistent basis sets, three-dimensional near-equilibrium potential energy functions (PEFs) have been calculated for the Xthinsp{sup 2}B{sub 1} and first excited {sup 2}A{sub 2} electronic states of the atmospherically important OClO and OBrO radicals. The analytical PEFs have been used in perturbational and variational calculations of the anharmonic spectroscopic constants and vibrational spectra of both species. Excellent agreement with the available experimental data are observed for both species and electronic states, e.g., the vibrational fundamental frequencies in the ground electronic states are reproduced to within about 5 cm{sup {minus}1}. For the Athinsp{sup 2}A{sub 2} state of OClO, it is demonstrated that the anomolously strong intensity of the {nu}{sub 3} mode in the UV absorption spectrum is due to strong anharmonic coupling between the stretching vibrations and not to a double minimum in the potential. Three-dimensional electric dipole moment functions have also been calculated for the ground electronic states of both species. These were used to calculate accurate absolute infrared absorption intensities for the fundamentals and low-lying overtones and combination bands of both species. {copyright} {ital 1998 American Institute of Physics.}

• OSTI ID: 664669
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 20 Vol. 109; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

66 PHYSICS
ATMOSPHERIC CHEMISTRY
CHLORINE OXIDES
DIPOLE MOMENTS
ELECTRONIC STRUCTURE
EXCITED STATES
GROUND STATES
INFRARED SPECTRA
OSCILLATOR STRENGTHS
OXYGEN COMPOUNDS
OZONE
PERTURBATION THEORY
POTENTIAL ENERGY
RADICALS
ULTRAVIOLET SPECTRA
VIBRATIONAL STATES