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Title: Franck-Condon simulation, including anharmonicity, of the photodetachment spectrum of P₂H‾: Restricted-spin coupled-cluster single-double plus perturbative triple and unrestricted-spin coupled-cluster single-double plus perturbative triple -F12x potential energy functions of P₂H and P₂H‾
Authors: Mok, Daniel K. W.
Lee, Edmond P. F.
Chau, Foo-tim
Dyke, John M.
Subjects: Coupled cluster calculations
Electron detachment
Franck-Condon factors
Free radicals
Negative ions
Organic compounds
Potential energy functions
Rotational states
STO calculations
Valence bands
Variational techniques
Vibrational states
Issue Date: 28-Sep-2011
Publisher: American Institute of Physics
Citation: Journal of chemical physics, 28 Sept. 2011, v. 135, no. 12, 124312, p. 1-11.
Abstract: Geometry optimization and harmonic vibrational frequency calculations have been carried out on the X˜²A' state of P₂H and the X˜¹A' state of P₂H‾ using the restricted-spin coupled-cluster single-double plus perturbative triple excitation [RCCSD(T)] and explicitly correlated unrestricted-spin coupledcluster single-double plus perturbative triple excitation [UCCSD(T)-F12x] methods. For RCCSD(T) calculations, basis sets of up to the augmented correlation-consistent polarized valence quintuple-zeta (aug-cc-pV5Z) quality were employed, and contributions from extrapolation to the complete basis set limit and from core correlation of the P2s²2p⁶ electrons were also included. For UCCSD(T)- F12x calculations, different atomic orbital basis sets of triple-zeta quality with different associated complementary auxiliary basis sets and different geminal Slater exponents were used. When the P 2s²2p⁶ core electrons were correlated in these F12x calculations, appropriate core-valence basis sets were employed. In addition, potential energy functions (PEFs) of the X˜²A' state of P₂H and the X˜¹A' state of P₂H‾ were computed at different RCCSD(T) and UCCSD(T)-F12x levels, and were used in variational calculations of anharmonic vibrational wavefunctions, which were then utilized to calculate Franck-Condon factors (FCFs) between these two states, employing a method which includes allowance for anharmonicity and Duschinsky rotation. The photodetachment spectrum of P₂H‾ was then simulated using the computed FCFs. Simulated spectra obtained using the RCCSD(T)/aug-cc-pV5Z and UCCSD(T)-F12x(x = a or b)/aug-cc-pCVTZ PEFs are compared and found to be essentially identical. Based on the computed FCFs, a more detailed assignment of the observed vibrational structure than previously reported, which includes “hot bands,” has been proposed. Comparison between simulated and available experimental spectra has been made, and the currently most reliable sets of equilibrium geometrical parameters for P₂H and its anion have been derived. The photodetachment spectrum of P₂D, yet to be recorded, has also been simulated.
Description: DOI: :10.1063/1.3640037
Rights: © 2011 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 D. K. W. Mok et al., J. Chem. Phys. 135, 124312 (2011) and may be found at http://link.aip.org/link/?jcp/135/124312.
Type: Journal/Magazine Article
URI: http://hdl.handle.net/10397/5057
ISSN: 0021-9606 (print)  
1089-7690 (online)
Appears in Collections:ABCT Journal/Magazine Articles

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