Electronic states and potential energy curves of SbF2 and SbF2+

Latifzadeh-Masoudipour, Lida; Balasubramanian, K.

doi:10.1016/s0009-2614(96)01117-7

Cited by 5 publications

(1 citation statement)

References 20 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Nevertheless, CASSCF/MRSDCI/RECP(3s3p2d) calculations on SbF 2 and its cation gave an AIE value of 8.22 eV (including Davidson correction) for SbF 2 . 38 In any case, the estimated AIE value of 8.5 eV for AsF 2 in ref. 10 was obtained assuming that the AIE value of AsF 2 should have a value in between those of PF 2 and BiF 2 , as expected from the trend of decreasing IE values down the group VA Pnictogen (Pn) elements: 39 N(14.5341 eV), 40 P(10.4867 eV), 41 As(9.7886 eV), 42 Sb(8.0064 eV) 43 and Bi(7.2855 eV) 44 .…”

Section: Discussionmentioning

confidence: 94%

Franck–Condon simulation of the photoelectron spectrum of AsF2 and the photodetachment spectrum of AsF2− using ab initio calculations: Ionization energy and electron affinity of AsF2

Mok

Lee

Chau

et al. 2010

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

RCCSD(T) and/or CASSCF/MRCI calculations were carried out on the X(2)B(1) state of AsF(2), the X(1)A(1), ã(3)B(1) and A(1)B(1) states of AsF(2)(+), and the X(1)A(1) state of AsF(2)(-) employing the fully-relativistic small-core effective core potential (ECP10MDF) for As and basis sets of up to augmented correlation-consistent polarized valence quintuple-zeta (aug-cc-pV5Z) quality. Minimum-energy geometrical parameters and relative electronic energies were evaluated, including contributions from extrapolation to the complete basis set limit and from outer core correlation of the As 3d(10) electrons. In addition, simplified, explicitly correlated RHF/UCCSD(T)-F12x calculations were also performed employing different atomic orbital basis sets, and associated complementary auxiliary and density-fitting basis sets. The best theoretical estimates of the adiabatic ionization energies (AIE(0)) of AsF(2)(X(2)B(1)) to the X(1)A(1) and ã(3)B(1) states of AsF(2)(+), including corrections for zero-point vibrational energy (DeltaZPE), are 9.099(8) and 13.290(22) eV respectively. The best estimated electron affinity (EA(0)) of AsF(2) is 1.182(16) eV, also including Delta(ZPE). These are currently the most reliable AIE(0) and EA(0) values for AsF(2). Potential energy functions (PEFs) of the X(2)B(1) state of AsF(2), the X(1)A(1) and ã(3)B(1) states of AsF(2)(+) and X(1)A(1) state of AsF(2)(-) were computed at RCCSD(T)/aug-cc-pV5Z, RCCSD(T)/aug-cc-pCV5Z and RHF/UCCSD(T)-F12a/aug-cc-pCVTZ levels. These PEFs were employed in variational calculations of anharmonic vibrational wavefunctions, which were then utilised to calculate Franck-Condon factors (FCFs), using a method which includes allowance for anharmonicity and Duschinsky rotation. The computed FCFs were used to simulate the first two bands in the photoelectron spectrum of AsF(2) and the first band in the photodetachment spectrum of AsF(2)(-), both yet to be recorded. The simulated spectra obtained using different sets of PEFs were found to be almost identical, suggesting that the simplified explicitly correlated UCCSD(T)-F12x method with a relatively small basis set can be a reliable alternative to the conventional RCCSD(T) correlation methods with a relatively large basis set, but at a significantly lower cost.

show abstract