Theoretical studies on spin-vibronic spectra of CH3 O(X2 E)

Zhang, Shiyang; Mo, Yuxiang

doi:10.7498/aps.60.027106

Acta Phys. Sin.

2011

DOI: 10.7498/aps.60.027106

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Theoretical studies on spin-vibronic spectra of CH3 O(X2 E)

Shiyang Zhang¹,

Yuxiang Mo²

Abstract: We made an ab initio study of the spin-vibronic couplings in CH3O (X2E) based on diabatic model. The diabatic potential energy curves were calculated at the level of CASPT2/cc-pvtz. The calculated spin-vibronic energy levels are compared with the experimental data, which indicates that the present calculation has higher accuracy than the previously reported ones.

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Cited by 2 publications

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Jahn-Teller effect in CH2DO/CHD2O(${\rm \tilde X}^{\rm 2} {\rm E}$X̃2E): Vibronic coupling of all vibrational modes

Shao

2013

The Journal of Chemical Physics

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For the Jahn-Teller active methoxy radical CH3O∕CD3O(X̃(2)E), only the degenerate vibrational modes break the C3v geometric symmetry. For the isotopologues CH2DO∕CHD2O, all their normal vibrational motions break the C3v geometric symmetry, which results in a splitting of the adiabatic potential energy surfaces (APESs), that is, all vibrational modes are Jahn-Teller active. Therefore, each fundamental vibrational energy level of CH2DO∕CHD2O splits into two levels due to a combination of Jahn-Teller and spin-orbit interactions. In this work we report an ab initio calculation of the spin-vibronic energy levels of CH3O∕CH2DO∕CHD2O∕CD3O using a diabatic model. The APESs were calculated at the UCCSD(T)-F12a∕cc-pVQ(T)Z-F12a level. The vibronic parameters in the diabatic model Hamiltonian of CD3O were first determined using the least-squares fitting to the APESs. The vibronic parameters of the other three isotopologues were derived from those of CD3O using the Duschinsky rotation method. The calculated spin-vibronic energy splittings for the vibrational ground states of CH3O∕CH2DO∕CHD2O∕CD3O are 61.8∕73.5∕70.2∕54.5 cm(-1), respectively, in good agreement with the reported experimental results.

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Jahn-Teller effect in CH2DO/CHD2O(${\rm \tilde X}^{\rm 2} {\rm E}$X̃2E): Vibronic coupling of all vibrational modes

Shao

2013

The Journal of Chemical Physics

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Infrared absorption spectra of partially deuterated methoxy radicals CH2DO and CHD2O isolated in solid para-hydrogen

Haupa

Johnson

Sibert

et al. 2017

The Journal of Chemical Physics

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The investigation of partially deuterated methoxy radicals is important because the symmetry lowering from C to C provides new insights into the couplings between rovibronic states via Jahn-Teller and spin-orbit interactions. The vibrational spectrum of the partially deuterated methoxy radical CHDO in a matrix of p-H has been recorded. This species was prepared by irradiating a p-H matrix containing deuterated d-nitritomethane (CHDONO) at 3.3 K with laser light at 355 nm. The identification of the radical is based on the photochemical behavior of the precursor and comparison of observed vibrational wavenumbers and infrared (IR) intensities with those predicted from a refined quartic, curvilinear, internal coordinate force field calculated with the coupled-cluster singles and doubles with perturbative triples/cc-pVTZ method. CHDO reacts with H with a rate coefficient (3.5 ± 1.0) × 10 s. Predominantly c-CHDOH and a negligibly small amount of t-CHDOH were produced. This stereoselectivity results from the reaction H + C-CHDOH, which was demonstrated by an additional experiment on irradiation of a CHDOH/Cl/p-H matrix with ultraviolet and IR light to induce the H + CHDOH reaction; only c-CHDOH was observed from this experiment. Even though the energies of transition states and products for the formation of c-CHDOH and t-CHDOH differ by only ∼10 cm, the selective formation of c-CHDOH can be explained by tunneling of the hydrogen atom via an optimal tunneling path. Similarly, the vibronic spectrum for the partially deuterated specie d-methoxy radical (CHDO) was obtained upon irradiation of d-nitritomethane (CHDONO) at 355 nm. Lines associated with the fundamental vibrational modes were observed and assigned; line positions agree with theoretically predicted vibrational wavenumbers. CHDO reacts with H with a rate coefficient (6.0 ± 1.4) × 10 s; CDOH was produced as a major product because the barrier for the formation of CHDOH from H + CHDOH is greater by ∼400 cm. Rate coefficients of the decays of CHO, CHDO, CHDO, and CDO and their corresponding potential energy surfaces are compared.

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Theoretical studies on spin-vibronic spectra of CH3 O(X2 E)

Cited by 2 publications

References 10 publications

Jahn-Teller effect in CH2DO/CHD2O(${\rm \tilde X}^{\rm 2} {\rm E}$X̃2E): Vibronic coupling of all vibrational modes

Jahn-Teller effect in CH2DO/CHD2O(${\rm \tilde X}^{\rm 2} {\rm E}$X̃2E): Vibronic coupling of all vibrational modes

Infrared absorption spectra of partially deuterated methoxy radicals CH2DO and CHD2O isolated in solid para-hydrogen

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