Vibronic interactions in NO3: from the 2E′ origin region to the NO + O2 reactive channel

Valachovic, L.; Riehn, Christoph; Mikhaylichenko, K.; Wittig, C.

doi:10.1016/0009-2614(96)00703-8

Cited by 10 publications

(5 citation statements)

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“…Several MH 3 systems were calculated, showing degenerate excited states with small JT distortions. Vibronic coupling in the radiationless decay of the 2 E‘ state of NO 3 is considered in ref .…”

Section: Mx3 Systemsmentioning

confidence: 99%

Modern Aspects of the Jahn−Teller Effect Theory and Applications To Molecular Problems

2001

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Section: Mx3 Systemsmentioning

confidence: 99%

Modern Aspects of the Jahn−Teller Effect Theory and Applications To Molecular Problems

2001

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“…The importance of the nitrate radical (NO 3 ) in atmospheric chemistry has generated widespread interest in its chemical and physical properties . In particular, the question of whether NO 3 possesses a D 3 h or C 2 v equilibrium structure has caused considerable controversy, with substantial experimental and theoretical support for each conclusion. − Ab initio calculations have emphasized the difficulty of the symmetry breaking problem in NO 3 by demonstrating that the potential energy surface is extremely flat in the region of the D 3 h minimum. − Even the most sophisticated levels of theory could not conclusively establish the nature of the D 3 h stationary point …”

Section: Introductionmentioning

confidence: 99%

Symmetry Breaking and the Molecular Structure of NO₃⁺

Miller

Francisco

2000

J. Phys. Chem. A

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The equilibrium structure and vibrational frequencies of the nitrate cation, NO 3 + , have been investigated with an extensive set of ab initio calculations. Two stationary points were identified on the NO 3 + potential energy surface: a symmetric D 3h structure and a C 2V ring structure similar to that found for the isoelectronic CO 3 molecule. Geometry optimizations executed at the CCSD(T)/aug-cc-pVTZ level of theory yielded the following data. NO 3. Calculations performed at the B3LYP, QCISD, CCSD, and CCSD(T) levels of theory all predict the C 2V structure to be lower in energy than the D 3h structure. Relative energy calculations performed with the Gaussian and complete basis set model chemistry algorithms also predict the C 2V structure to be the most stable NO 3 + conformation. These results are supported by vibrational frequency calculations which suggest that the D 3h structure may correspond to a second-order saddle point rather than a true minimum on the NO 3 + potential energy hypersurface. The symmetry breaking observed in the present NO 3 + calculations is similar to that observed in ab initio studies of the NO 3 equilibrium structure and is used to examine symmetry breaking across the nitrate series NO 3 -, NO 3 , NO 3 + . † Part of the special issue "Harold Johnston Festschrift".

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“…The dynamics of the NO 3 radical including the dissociation processes have recently been investigated extensively. [31][32][33][34][35][36] In these studies the importance of vibronic interactions in NO 3 was stressed. Nizkorodov et al 37 observed formation of NO 3 when NO 2 was excited at 436.45 nm.…”

Section: Introductionmentioning

confidence: 99%

Near-infrared band of the nitrate radical NO3 observed by diode laser spectroscopy

Hirota

Ishiwata

Kawaguchi

et al. 1997

The Journal of Chemical Physics

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Articles you may be interested inHigh-resolution laser spectroscopy and magnetic effect of the B ̃ 2E′ ← X ̃ 2A2′ transition of 14NO3 radical Electronic states, conical intersections, and spin-rovibronic spectroscopy of the nitrogen oxide sulfide radical J. Chem. Phys. 138, 104318 (2013); 10.1063/1.4794313High-resolution cavity ringdown spectroscopy of the jet-cooled ethyl peroxy radical C 2 H 5 O 2Time-resolved infrared diode laser spectroscopy of the ν1 band of the iron carbonyl radical (FeCO) produced by the ultraviolet photolysis of Fe(CO)5We have analyzed the near-infrared band of NO 3 observed at 7602 cm Ϫ1 by using diode laser spectroscopy. Most of the spectral lines were recorded using source-frequency modulation. Zeeman modulation was found useful in selectively detecting some Q branch lines, which provided us with a clue to the assignment of the observed spectra. The band satisfied selection rules for a parallel band and was thus ascribed to a 2 A 1 Љ -2 A 2 Ј vibronic component associated with the 2 EЉ -X 2 A 2 Ј electronic transition, namely, to a transition from the ground vibronic state to the A 1 Љ vibronic state resulting from excitation of the degenerate in-plane bending mode in the 2 EЉ electronically excited state manifold. The band was almost free of perturbations, except for some Kϭ6 lines. The least-squares analysis of 581 assigned lines led to molecular parameters of the upper state, where ground-state parameters were fixed to those obtained from the infrared study previously reported ͓K.Kawaguchi, E. Hirota, T. Ishiwata, and I. Tanaka, J. Chem. Phys. 93, 951 ͑1990͔͒. The upper-state B rotational constant gave the effective N-O distance of 1.271 Å, which is to be compared with 1.240 Å in the ground vibronic state. The ⑀ bb spin-rotation interaction constant of the upper state was close in magnitude to that in the ground vibronic state, but of opposite sign. This observation indicates that the spin-rotation interaction is primarily caused by that between the 2 EЉ excited and the ground electronic states.

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Vibronic interactions in NO3: from the 2E′ origin region to the NO + O2 reactive channel

Cited by 10 publications

References 20 publications

Modern Aspects of the Jahn−Teller Effect Theory and Applications To Molecular Problems

Modern Aspects of the Jahn−Teller Effect Theory and Applications To Molecular Problems

Symmetry Breaking and the Molecular Structure of NO₃⁺

Near-infrared band of the nitrate radical NO3 observed by diode laser spectroscopy

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Vibronic interactions in NO3: from the 2E′ origin region to the NO + O2 reactive channel

Cited by 10 publications

References 20 publications

Modern Aspects of the Jahn−Teller Effect Theory and Applications To Molecular Problems

Modern Aspects of the Jahn−Teller Effect Theory and Applications To Molecular Problems

Symmetry Breaking and the Molecular Structure of NO3+

Near-infrared band of the nitrate radical NO3 observed by diode laser spectroscopy

Contact Info

Product

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Symmetry Breaking and the Molecular Structure of NO₃⁺