Tunneling splittings in vibronic energy levels of ${\rm CH}_{\rm 3} {\rm F}^{\rm + } \left( {{\rm \tilde X}{}^{\rm 2}{\rm E}} \right)$ CH 3F+X̃2E studied by high resolution photoelectron spectroscopy and <i>ab initio</i> calculation

Gao, Shunliang; Dai, Zuyang; Sun, Weidong; Li, Hua; Wang, Jia; Mo, Yuxiang

doi:10.1063/1.4817201

Cited by 20 publications

(10 citation statements)

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“…30 After taking into account the Jahn−Teller (JT) effect, the degenerate 2 E electronic state splits to one 2 A′ and one 2 A″ state (C s symmetry). 30,31 As displayed in Figure 1, the potential energy curves show that the X 2 E ground state is bound along the C−F coordinate and its two JT split states 1 2 A″ and 1 2 A′ are almost degenerate. The A 2 A 1 (2 2 A′) excited state was calculated to be a repulsive state, although a shallow well may exist along its dissociation pathway.…”

Section: Introductionmentioning

confidence: 98%

CH₃⁺ Formation in the Dissociation of Energy-Selected CH₃F⁺ Studied by Double Imaging Electron/Ion Coincidences

2015

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The dissociation of energy-selected methyl fluoride ion CH3F(+) along the CH3(+) and F formation channel has been investigated in detail in the 12.2-19.8 eV energy range. Three low-lying electronic states of the CH3F(+) ion, X(2)E, A(2)A1, and B(2)E, were prepared and analyzed by the method of double imaging photoelectron photoion coincidence (i(2)PEPICO). Three types of CH3(+) fragment ions corresponding to the dissociation of X(2)E, A(2)A1, and B(2)E electronic states have been observed and identified through their kinetic energy release distribution (KERD) curves, showing that the dissociation of the CH3F(+) ion in the different electronic states along the CH3(+) formation channel is state-specific, even outside of the Franck-Condon region. Highly excited vibrational levels of the X(2)E ground state can be populated through a resonant or near-resonant autoionization process and undergo vibrational predissociation into CH3(+) fragment ions. The A(2)A1 first excited state is repulsive along the F-loss coordinate, and its dissociation is direct and fast. The CH3F(+) ions in the B(2)E excited state first undergo an internal conversion toward the hot cation ground state X(2)E and then statistically dissociate into CH3(+) and F fragments.

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Section: Introductionmentioning

confidence: 98%

CH₃⁺ Formation in the Dissociation of Energy-Selected CH₃F⁺ Studied by Double Imaging Electron/Ion Coincidences

2015

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“…Two electronic states, 2 B 2g and 2 B 1g , were examined for Bz + . The initial density matrixes for these states were obtained by the complete active space self-consistent filed (CASSCF) method with five electrons distributed into six orbitals, namely, CASSCF (5,6). Using the density matrix (the initial guess), the trajectories for the benzene radical cations at the 2 B 2g and 2 B 1g states were then propagated at the MP2/6-311++G(d,p) level.…”

Section: Computational Detailsmentioning

confidence: 99%

Jahn–Teller Effect of the Benzene Radical Cation: A Direct ab Initio Molecular Dynamics Study

Tachikawa

2018

J. Phys. Chem. A

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The benzene radical cation (Bz) is a typical model molecule of the Jahn-Teller (J-T) active species. Bz has two structural forms due to the J-T effect. These are the compressed and elongated forms, expressed as Bz(comp) and Bz(elong), respectively. In Bz(comp), the hexagonal structure of the benzene ring is compressed up and down, and in Bz(elong), it is pulled up and down. From electron spin resonance experiments, it was found that Bz takes a compressed form in low-temperature Freon matrices (CFCl and CFClCFCl), whereas the elongated form was found in argon matrices. However, the selectivity of these structural forms is still unclear. In this study, the ionization dynamics of isolated benzene (Bz) and benzene-M complexes (where M denotes counter-molecules, M = NH, HO, CFCl, CH, CHOH, Ar, SH, ammonia dimer, or water dimer) have been investigated by means of the direct ab initio molecular dynamics (AIMD) method in order to shed light on the Bz formation mechanism. The static ab initio calculations showed that Bz(comp) is slightly more energetically stable than Bz(elong), although the energy difference was only 0.1 kcal/mol at the CCSD/6-311++G(d,p) level. The direct AIMD calculations indicated that Bz(comp) was formed from the Bz-M complexes when M was NH, CFCl, or an ammonia dimer, whereas the ionization of Bz-M when M was HO, CH, CHOH, SH or a water dimer formed Bz(elong). In the case of complexes with an argon dimer, Bz(Ar), both forms were obtained from a slight orientation change of Ar on Bz. A selective rule is discussed on the basis of the calculated results.

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“…43 Recently, this model has been successfully developed to calculate the vibronic energy levels of polyatomic molecules with C 3v symmetry. 39,40,[44][45][46][47][48][49][50] One of the key features of this method is that the diabatic potential energy surfaces are expressed by Taylor expansions with normal coordinates as variables. This method has been extended to linear molecule in previous work, which enables us to compute the spin-vibronic energy levels of linear BrCN + (X 2 Π).…”

Section: A Diabatic Modelmentioning

confidence: 99%

“…A semi-empirical simulation method was employed to determine the IE as we have done previously. 49,50 The rotational energy levels for HCCCl + X 2 Π are calculated according to 55…”

Section: B First Adiabatic Ie Of Hccclmentioning

confidence: 99%

The Renner-Teller effect in HCCCl+(X̃2Π) studied by zero-kinetic energy photoelectron spectroscopy and ab initio calculations

Sun

Dai

Wang

et al. 2015

The Journal of Chemical Physics

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The spin-vibronic energy levels of the chloroacetylene cation up to 4000 cm(-1) above the ground state have been measured using the one-photon zero-kinetic energy photoelectron spectroscopic method. The spin-vibronic energy levels have also been calculated using a diabatic model, in which the potential energy surfaces are expressed by expansions of internal coordinates, and the Hamiltonian matrix equation is solved using a variational method with harmonic basis functions. The calculated spin-vibronic energy levels are in good agreement with the experimental data. The Renner-Teller (RT) parameters describing the vibronic coupling for the H-C≡C bending mode (ε4), Cl-C≡C bending mode (ε5), the cross-mode vibronic coupling (ε45) of the two bending vibrations, and their vibrational frequencies (ω4 and ω5) have also been determined using an effective Hamiltonian matrix treatment. In comparison with the spin-orbit interaction, the RT effect in the H-C≡C bending (ε4) mode is strong, while the RT effect in the Cl-C≡C bending mode is weak. There is a strong cross-mode vibronic coupling of the two bending vibrations, which may be due to a vibronic resonance between the two bending vibrations. The spin-orbit energy splitting of the ground state has been determined for the first time and is found to be 209 ± 2 cm(-1).

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Tunneling splittings in vibronic energy levels of ${\rm CH}_{\rm 3} {\rm F}^{\rm + } \left( {{\rm \tilde X}{}^{\rm 2}{\rm E}} \right)$ CH 3F+X̃2E studied by high resolution photoelectron spectroscopy and ab initio calculation

Cited by 20 publications

References 32 publications

CH₃⁺ Formation in the Dissociation of Energy-Selected CH₃F⁺ Studied by Double Imaging Electron/Ion Coincidences

CH₃⁺ Formation in the Dissociation of Energy-Selected CH₃F⁺ Studied by Double Imaging Electron/Ion Coincidences

Jahn–Teller Effect of the Benzene Radical Cation: A Direct ab Initio Molecular Dynamics Study

The Renner-Teller effect in HCCCl+(X̃2Π) studied by zero-kinetic energy photoelectron spectroscopy and ab initio calculations

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Tunneling splittings in vibronic energy levels of ${\rm CH}_{\rm 3} {\rm F}^{\rm + } \left( {{\rm \tilde X}{}^{\rm 2}{\rm E}} \right)$ CH 3F+X̃2E studied by high resolution photoelectron spectroscopy and ab initio calculation

Cited by 20 publications

References 32 publications

CH3+ Formation in the Dissociation of Energy-Selected CH3F+ Studied by Double Imaging Electron/Ion Coincidences

CH3+ Formation in the Dissociation of Energy-Selected CH3F+ Studied by Double Imaging Electron/Ion Coincidences

Jahn–Teller Effect of the Benzene Radical Cation: A Direct ab Initio Molecular Dynamics Study

The Renner-Teller effect in HCCCl+(X̃2Π) studied by zero-kinetic energy photoelectron spectroscopy and ab initio calculations

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CH₃⁺ Formation in the Dissociation of Energy-Selected CH₃F⁺ Studied by Double Imaging Electron/Ion Coincidences

CH₃⁺ Formation in the Dissociation of Energy-Selected CH₃F⁺ Studied by Double Imaging Electron/Ion Coincidences