On the vibronic level structure in the NO3 radical : Part III. Observation of intensity borrowing via ground state mixing

“…60 The vibronic coupling problem of the ground state has been treated successfully before 61,62 within the linear vibronic coupling approach but no extended PES has been developed. The treatment of the first excited state was by far less satisfactory [63][64][65][66] and thus this state will be our main target of the present study. This first excited state of 2 E symmetry, though predicted before theoretically, 67 was first observed in a photoelectron detachment spectrum in 1991.…”

Section: Introductionmentioning

confidence: 99%

Full-dimensional diabatic potential energy surfaces including dissociation: The 2E″ state of NO3

Eisfeld

Vieuxmaire

Viel

2014

The Journal of Chemical Physics

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A scheme to produce accurate full-dimensional coupled diabatic potential energy surfaces including dissociative regions and suitable for dynamical calculations is proposed. The scheme is successfully applied to model the two-sheeted surface of the (2)E″ state of the NO3 radical. An accurate potential energy surface for the NO₃⁻ anion ground state is developed as well. Both surfaces are based on high-level ab initio calculations. The model consists of a diabatic potential matrix, which is expanded to higher order in terms of symmetry polynomials of symmetry coordinates. The choice of coordinates is key for the accuracy of the obtained potential energy surfaces and is discussed in detail. A second central aspect is the generation of reference data to fit the expansion coefficients of the model for which a stochastic approach is proposed. A third ingredient is a new and simple scheme to handle problematic regions of the potential energy surfaces, resulting from the massive undersampling by the reference data unavoidable for high-dimensional problems. The final analytical diabatic surfaces are used to compute the lowest vibrational levels of NO₃⁻ and the photo-electron detachment spectrum of NO₃⁻ leading to the neutral radical in the (2)E″ state by full dimensional multi-surface wave-packet propagation for NO3 performed using the Multi-Configuration Time Dependent Hartree method. The achieved agreement of the simulations with available experimental data demonstrates the power of the proposed scheme and the high quality of the obtained potential energy surfaces.

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“…15 Despite the importance of CO 3 , relatively few studies have been dedicated to this molecule, especially when compared to NO 3 , which has one more electron and also features rich Jahn-Teller (JT) and pseudo-Jahn-Teller (pJT) interactions. [16][17][18][19][20][21][22][23][24][25] Only till two years ago, the first vibronic spectrum of CO 3 was obtained using the negative ion photoelectron (NIPE) spectroscopic technique in a work participated by two of us (B.C. and X.B.W.).…”

Section: Introductionmentioning

confidence: 99%

Vibronic interaction in CO₃⁻ photo-detachment: Jahn–Teller effects beyond structural distortion and general formalisms for vibronic Hamiltonians in trigonal symmetries

Seidu

Goel

Wang

et al. 2019

Phys. Chem. Chem. Phys.

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Recently, the negative ion photoelectron spectrum of CO − 3 was reported and the second lowest energy band is assigned to the close-lying 3 E and 3 E states that undergo Jahn-Teller distortions (Chem. Sci., 2016, 7, 1142. This assignment is based on the Born-Oppenheimer approximation and the assumption of a static Jahn-Teller effect that distorts the CO 3 structure from D 3h to C 2v symmetry. In this work, we employ a 4 states 6 modes vibronic coupling model to investigate the triplet band and uncover the dynamic and non-adiabatic nature of the Jahn-Teller and pseudo-Jahn-Teller interactions in the triplet states. The apparent four peaks progression in the band is studied in depth, and is found to consist of more than four transitions. By comparing the simulated spectra using the full model and the reduced-dimension 2 states 2 modes models, we characterize those transitions. The origin of the complexities of the spectrum is traced to the C-O nonbonding character of the orbitals that lose electron in the photo-detachment process. Methodology-wise, we derive and present the formalisms for arbitrary order expansions of all bimodal trigonal Jahn-Teller and pseudo-Jahn-Teller Hamiltonians in vibrational coordinates.

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On the vibronic level structure in the NO3 radical : Part III. Observation of intensity borrowing via ground state mixing

Cited by 29 publications

References 18 publications

Theoretical study of the excitation spectrum of azomethane

Theoretical study of the excitation spectrum of azomethane

Full-dimensional diabatic potential energy surfaces including dissociation: The 2E″ state of NO3

Vibronic interaction in CO₃⁻ photo-detachment: Jahn–Teller effects beyond structural distortion and general formalisms for vibronic Hamiltonians in trigonal symmetries

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On the vibronic level structure in the NO3 radical : Part III. Observation of intensity borrowing via ground state mixing

Cited by 29 publications

References 18 publications

Theoretical study of the excitation spectrum of azomethane

Theoretical study of the excitation spectrum of azomethane

Full-dimensional diabatic potential energy surfaces including dissociation: The 2E″ state of NO3

Vibronic interaction in CO3− photo-detachment: Jahn–Teller effects beyond structural distortion and general formalisms for vibronic Hamiltonians in trigonal symmetries

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Vibronic interaction in CO₃⁻ photo-detachment: Jahn–Teller effects beyond structural distortion and general formalisms for vibronic Hamiltonians in trigonal symmetries