A combined ab initio and Franck‐Condon factor simulation study on the photodetachment spectrum of ScO2−

Restricted‐spin coupled‐cluster single‐double plus perturbative triple excitation {RCCSD(T)} potential energy functions (PEFs) of the $ \tilde X $2B2 state of ScO2 and the $ \tilde X $1A1 state of ScO2− were computed, employing the augmented correlation‐consistent polarized‐weighted core‐valence quadruple‐zeta (aug‐cc‐pwCVQZ) basis set for Sc and augmented correlation‐consistent polarized valence quadruple‐zeta (aug‐cc‐pVQZ) basis set for O, and with the outer core Sc 3s23p6 electrons being explicitly correlated. Franck‐Condon factors, which include allowance for Duschinsky rotation and anharmonicity, were calculated using the computed RCCSD(T) PEFs, and were used to simulate the first photodetachment band of ScO2−. The simulated spectrum matches well with the corresponding experimental 355 nm photodetachment spectrum of Wu and Wang, J Phys Chem A 1998, 102, 9129, confirming the assignment of the photodetachment spectrum and the reliability of the RCCSD(T) PEFs used. Further calculations on low‐lying electronic states of ScO2 gave adiabatic relative electronic energies (Te's) of, and vertical excitation energies (Tv's) to, the $ \tilde A $2A1, $ \tilde B $2B1, and $ \tilde C $2A2 states of ScO2 (from the $ \tilde X $2B2 state of ScO2), as well as electron affinities (EAs) and vertical detachment energies (VDEs) to these neutral states from the $ \tilde X $1A1 state of ScO2−. © 2008 Wiley Periodicals, Inc. J Comput Chem, 2009

[1]  Mingfei Zhou,et al.  Formation and characterization of the oxygen-rich scandium oxide/dioxygen complexes ScOn (n = 4, 6, 8) in solid argon. , 2007, The journal of physical chemistry. A.

[2]  Alkali and alkaline earth metal compounds: core—valence basis sets and importance of subvalence correlation , 2003, physics/0301056.

[3]  Avelino Corma,et al.  Inorganic Solid Acids and Their Use in Acid-Catalyzed Hydrocarbon Reactions , 1995 .

[4]  Edmond P. F. Lee,et al.  Potential energy functions of the X̃ 2B1, Ã 2B2, B̃ 2A1, and C̃ 2A2 states of Cl2O+ and the X̃ 1A1 state of Cl2O: Franck–Condon simulations of photoelectron bands of Cl2O which include anharmonicity , 2003 .

[5]  J. Watson.  Simplification of the molecular vibration-rotation hamiltonian , 2002 .

[6]  Manuela Merchán,et al.  Density matrix averaged atomic natural orbital (ANO) basis sets for correlated molecular wave functions , 1995 .

[7]  Edmond P. F. Lee,et al.  The X̃ 2B1, 2B2, 2A1, and 2A2 states of oxygen difluoride cation (F2O+): High-level ab initio calculations and simulation of the ultraviolet photoelectron spectrum of F2O , 2001 .

[8]  Jürgen Gauss,et al.  Coupled‐cluster methods with noniterative triple excitations for restricted open‐shell Hartree–Fock and other general single determinant reference functions. Energies and analytical gradients , 1993 .

[9]  Kirk A Peterson,et al.  Systematically convergent basis sets for transition metals. I. All-electron correlation consistent basis sets for the 3d elements Sc-Zn. , 2005, The Journal of chemical physics.

[10]  A. Wachters,et al.  Gaussian Basis Set for Molecular Wavefunctions Containing Third‐Row Atoms , 1970 .

[11]  Edmond P. F. Lee,et al.  A new method of calculation of Franck-Condon factors which includes allowance for anharmonicity and the Duschinsky effect: Simulation of the He I photoelectron spectrum of ClO 2 , 2000 .

[12]  Markus Reiher,et al.  Exact decoupling of the Dirac Hamiltonian. I. General theory. , 2004, The Journal of chemical physics.

[13]  Henry F. Schaefer,et al.  Analyses of the ScO− and ScO2− photoelectron spectra , 2000 .

[14]  Hans-Joachim Werner,et al.  A comparison of the efficiency and accuracy of the quadratic configuration interaction (QCISD), coupled cluster (CCSD), and Brueckner coupled cluster (BCCD) methods , 1992 .

[15]  M. Rosi,et al.  The vibrational frequencies of CaO2, ScO2, and TiO2: a comparison of theoretical methods , 1998 .

[16]  B. K. Rao,et al.  Systematic Study of Oxo, Peroxo, and Superoxo Isomers of 3d-Metal Dioxides and Their Anions , 2000 .

[17]  Edmond P. F. Lee,et al.  Simulation of ù B₁→ X˜¹A₁CF₂single vibronic level emissions : including anharmonic and Duschinsky effects , 2001 .

[18]  W. R. Moser,et al.  Homogeneous transition metal catalyzed reactions , 1992 .

[19]  Marzio Rosi,et al.  Reactions of Laser-Ablated Scandium Atoms with Dioxygen. Infrared Spectra of ScO, OScO, (O2)ScO, (ScO)2, and Sc(O2)2 in Solid Argon , 1997 .

[20]  Hongbin Wu,et al.  Photoelectron Spectroscopy and Electronic Structure of ScOn- (n = 1−4) and YOn- (n = 1−5): Strong Electron Correlation Effects in ScO-and YO- , 1998 .