Theoretical study on spectroscopic properties and predissociation mechanisms of the electronic states of carbon monofluoride

Wei, Xing; Liu, Hui; Shi, Deheng; Sun, Jinfeng; Zun-L, Zhu; Shu-Xia, L

doi:10.7498/aps.64.153101

Cited by 3 publications

(1 citation statement)

References 43 publications

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“…The energy gaps among these three dissociation limits are also consistent with the energy gap between CF( 2 Π ) and CF( 4 Σ − ) (3.54 eV), and the energy gap between CF( 4 Σ − ) and CF( 2 Δ) (2.64 eV). [40] The ground state X and the lowest triplet ã state are bound states with the respective dissociation energies 2.82 eV and 1.36 eV, respectively, while the Ã state is a predissociative state. There are two different barriers on the Ã state PEC of CFCl, one leading to dissociation to the CCl+F fragments and the other barrier to linearity for this generic bent molecule.…”

Section: State Vte (Ev) Oscillator Strength Main Configuration Excita...mentioning

confidence: 99%

Examination of Potential Energy Curves of CFCl by Multi-reference Configuration Interaction Method

Sun

Liu

Ren

et al. 2015

Chinese Phys. Lett.

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We give a detailed examination of potential energy curves of the singlet and triplet states of CFCl correlated with the lowest three dissociation limits. The calculations are carried out at the internally contracted multireference configuration interaction/cc-pV(T+d)Z level with the other two geometric parameters fixed at the X state equilibrium conformation. The vertical transition energy, the oscillator strength, the main configuration and the electron transition are also investigated at the same level.

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Section: State Vte (Ev) Oscillator Strength Main Configuration Excita...mentioning

confidence: 99%

Examination of Potential Energy Curves of CFCl by Multi-reference Configuration Interaction Method

Sun

Liu

Ren

et al. 2015

Chinese Phys. Lett.

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icMRCI+Q study on spectroscopic properties of twelve -S states and twenty-three states of the CF+ cation

Wei¹,

Liu²,

Shi³

et al. 2016

Acta Phys. Sin.

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The potential energy curves of twenty-three states generated from the twelve -S states (X1+, a3, 13+, 13, 11, 11-, 13-, 21+, 11, 23, 21 and 23+) correlating with the first dissociation channel C+(2Pu)+ F(2Pu) of the CF+ cation are obtained by using the internally contracted multireference configuration interaction approach with the Davidson modification (icMRCI+Q) on the basis of the correlation-consistent aug-cc-pV5Z and aug-cc-pV6Z basis sets for the first time. The spin-orbit coupling, core-valence correlation and relativistic corrections are taken into account, and all the potential energy curves are extrapolated to the complete basis set limit by separately extrapolating the Hartree-Fock and correlation energies scheme. Based on the calculated potential energy curves, the spectroscopic parameters of the bound and quasibound nine -S and sixteen states of the CF+ cation are obtained. And the spectroscopic parameters of X1+and a31st well-S states which are in very good agreement with experimental results are achieved. Furthermore, the vertical and adiabatic ionization potentials of ionization from the X2 state of CF radical to the bound and quasibound nine -S states of the CF+ cation are calculated, and the vertical and adiabatic ionization potentials of the CF+(X1+) CF(X2 ) and CF+(a31st well) CF(X2 ) ionizations are also in good agreement with the corresponding experimental values. Various curve crossings of -S states are revealed, and with the help of our computed spin-orbit coupling matrix elements, the predissociation mechanisms of the a31st well, 111st well and 21+ states are analyzed for the first time. The spin-orbit-induced predissociations for the a31st well, 111st well and 21+-S states could happen, and the predissociations of the a31st well, 111st well and 21 +-S states start around the vibrational levels ' = 15, ' = 1 and ' = 1, respectively. Relative energies of the twenty-three states in the dissociation limits are given, and our calculations match the experimental results very well. Finally, the Franck-Condon factors and radiative lifetimes of transitions from (2) 0+1st well (;'=05), (1) 11st well ('=05) and (2) 11st well ('=0) to X0+ states are predicted for the future laboratory research.

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icMRCI+Q study on spectroscopic properties and predissociation mechanisms of electronic states of BF+ cation

Xing¹,

Sun²,

Shi³

et al. 2018

Acta Phys. Sin.

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In this paper, we study the spectroscopic properties and predissociation mechanisms of 14 states, which come from the first two dissociation channels of the BF+ cation. The potential energy curves of 14 Λ-S (X2Σ+, 12Π, 22Π, 22Σ+, 14Σ+, 14Δ, 14Σ1, 12Δ, 12Σ1, 32Σ+, 14Π, 24Π, 24Σ+, and 32Π) and corresponding 30 Ω states are calculated using the complete active space self-consistent field method, which is followed by the valence internally contracted multireference configuration interaction approach with the Davidson modification. To improve the reliability and accuracy of the potential energy curves, the core-valence correlation and scalar relativistic corrections, as well as the extrapolation of potential energy to the complete basis set limit are taken into account. The spin-orbit coupling is computed using the state interaction approach with the Breit-Pauli Hamiltonian. Based on these potential energy curves, the spectroscopic parameters and vibrational levels are determined for all the bound and quasi-bound Λ-S and Ω states. The present ground-state spectroscopic constants match well with the available experimental data. In addition, the vertical and adiabatic ionization potentials from the X1Σ+ state of BF molecule to the X2Σ+, 12Π, and 22Σ+ states of BF+ cation are calculated. The results of BF+(X2Σ+) ← BF(X1Σ+) ionization are in good agreement with the measurements. Various curve crossings of Λ-S states are revealed. We calculate the spin-orbit matrix elements between two interacting electronic states in the curve crossing region. With the help of present spin-orbit coupling matrix elements, we analyze the predissociation mechanisms of X2Σ+ and 32Π states along with the perturbations of the nearby states to 22Π, 14Σ+ and 32Σ+ states for the first time. The predissociation of X2Σ+ and 32Π states have a chance to occur around the vibrational levels υ"=30 and υ'=0 due to spin-orbit coupling, respectively. The present results also indicate that the υ' ≥ 9 vibrational levels of 22Π state are perturbed by the crossing states 22Σ+, 14Σ+, 14Δ, 14Σ1, 12Δ, 12Σ1, 32Σ+, and 14Π, that the υ' ≥ 4 vibrational levels of 14Σ+ state are perturbed via the interacting states 14Σ1 and 12Σ1, and the great perturbations between υ' ≥ 4 vibrational levels of 32Σ+ state and υ' ≥ 0 vibrational levels of 14Π state. For the 30 Ω state, we also calculate the relative energies of dissociation limits compared with the lowest one matching well with the experimental ones. Finally, the Franck-Condon factors, Einstein coefficients, and radiative lifetimes are evaluated for the 22Π (υ'=0-9)-X2Σ+, 22Σ+ (υ'=0-2)-X2Σ+, (3)1/2-(1)1/21st well, and (2)3/2 (υ'=0-9)-(1)1/21st well transitions.

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Theoretical study on spectroscopic properties and predissociation mechanisms of the electronic states of carbon monofluoride

Cited by 3 publications

References 43 publications

Examination of Potential Energy Curves of CFCl by Multi-reference Configuration Interaction Method

Examination of Potential Energy Curves of CFCl by Multi-reference Configuration Interaction Method

icMRCI+Q study on spectroscopic properties of twelve -S states and twenty-three states of the CF+ cation

icMRCI+Q study on spectroscopic properties and predissociation mechanisms of electronic states of BF+ cation

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