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Title: Ab initio calculations on the X˜¹A' and ùA" states of HPO and Franck-Condon simulation of the single vibronic level emission spectra of HPO and DPO
Authors: Lee, EPF
Mok, DKW 
Chau, FT
Dyke, JM
Issue Date: 7-Dec-2007
Source: Journal of chemical physics, 7 Dec. 2007, v. 127, no. 21, 214305, p. 1-12
Abstract: Minimum-energy geometries and relative electronic energies of the X˜¹A' and ùA" states of HPO have been computed employing the coupled-cluster single-double plus perturbative triple excitations {RCCSD(T)} and/or complete-active-space self-consistent-field (CASSCF) multireference internally contracted configuration interaction (MRCI) methods with basis sets of up to the augmented correlation-consistent polarized-valence quintuple-zeta (aug-cc-pV5Z) quality. In addition, RCCSD(T)/aug-cc-pVQZ and CASSCF/MRCI/aug-cc-pVQZ potential energy functions, anharmonic vibrational wave functions, and energies involving all three vibrational modes for both electronic states of HPO and DPO, and Franck-Condon factors between the two electronic states, which allow for Duschinsky rotation and anharmonicity, were computed. Computed Franck-Condon factors were then used to simulate single vibronic level (SVL) emission spectra recently reported by Tackett and Clouthier [J. Chem. Phys. 117, 10604 (2002)]. Excellent agreement between the simulated and observed spectra was obtained for the X ˜¹A"(1,0,0) → X ˜¹A' SVL emission of HPO and DPO, when the best estimated ab initio geometries of the two states, which include contributions from core correlation and extrapolation to the complete basis set limit, were used in the simulation, suggesting that the best estimated ab initio geometry of the ùA" state of HPO, particularly the bond angle of 94.5°, is more reliable than the available experimentally derived geometry. A discussion on the geometrical parameters derived from rotational constants obtained from the rotational analysis of a high-resolution spectrum and from Franck-Condon simulation of the vibrational structure of an electronic spectrum is given.
Keywords: Ab initio calculations
Bond angles
bond lengths
Configuration interactions
Coupled cluster calculations
Franck-Condon factors
Luminescence
Molecular electronic states
Potential energy functions
Rotational states
SCF calculations
Vibrational states
Vibronic states
Publisher: American Institute of Physics
Journal: Journal of chemical physics 
ISSN: 0021-9606
EISSN: 1089-7690
DOI: 10.1063/1.2790892
Rights: © 2007 American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics. The following article appeared in E. P. F. Leee et al., J. Chem. Phys. 127, 214305 (2007) and may be found at http://link.aip.org/link/?jcp/127/214305.
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