Photochemistry of Ozone: Surprises and Recent Lessons

Ravishankara, A. R.; Hancock, Gus; Kawasaki, Masahiro; Matsumi, Yutaka

doi:10.1126/science.280.5360.60

Cited by 93 publications

(87 citation statements)

References 9 publications

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“…[1][2][3][4] The spin-forbidden quenching O( 1 D) + N 2 (X 1 + g ) → O( 3 P ) + N 2 (X 1 + g ) and predissociation N 2 O(X 1 + ) → N 2 (X 1 + g ) + O( 3 P ) processes are essentially due to the spin-orbit couplings between the ground X 1 + and the excitedã 3 A andb 3 A electronic states of N 2 O. Because the quenching reaction is a major process in the O( 1 D) atmospheric removal, it was extensively investigated both experimentally and theoretically.…”

Section: Introductionmentioning

confidence: 99%

Nonadiabatic dynamics of O(1D) + N2$( {X{}^1\Sigma _g^ + } )\rightarrow $(XΣg+1)→O(3P) + N2$ ( {X{}^1\Sigma _g^ + } )$(XΣg+1) on three coupled potential surfaces: Symmetry, Coriolis, spin-orbit, and Renner-Teller effects

Defazio

Gamallo

Petrongolo

2012

The Journal of Chemical Physics

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We present the spin-orbit (SO) and Renner-Teller (RT) quantum dynamics of the spin-forbidden quenching O((1)D) + N(2)(X(1)Σ(g)(+)) → O((3)P) + N(2)(X(1)Σ(g)(+)) on the N(2)O X(1)A', ã(3)A", and b(3)A' coupled PESs. We use the permutation-inversion symmetry, propagate coupled-channel (CC) real wavepackets, and compute initial-state-resolved probabilities and cross sections σ(j(0)) for the ground vibrational and the first two rotational states of N(2), j(0) = 0 and 1. Labeling symmetry angular states by j and K, we report selection rules for j and for the minimum K value associated with any electronic state, showing that ã(3)A" is uncoupled in the centrifugal-sudden (CS) approximation at j(0) = 0. The dynamics is resonance-dominated, the probabilities are larger at low K, σ(j(0)) decrease with the collision energy and increase with j(0), and the CS σ(0) is lower than the CC one. The nonadiabatic interactions play different roles on the quenching dynamics, because the X(1)A'-b(3)A' SO effects are those most important while the ã(3)A"-b(3)A' RT ones are negligible.

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Section: Introductionmentioning

confidence: 99%

Nonadiabatic dynamics of O(1D) + N2$( {X{}^1\Sigma _g^ + } )\rightarrow $(XΣg+1)→O(3P) + N2$ ( {X{}^1\Sigma _g^ + } )$(XΣg+1) on three coupled potential surfaces: Symmetry, Coriolis, spin-orbit, and Renner-Teller effects

Defazio

Gamallo

Petrongolo

2012

The Journal of Chemical Physics

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“…[4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21][22][23] The electronic structure of ozone is known to be complicated. 1 It has been experimentally studied in great detail over several decades 2,3 and is still under intense investigation.…”

Section: Introductionmentioning

confidence: 99%

The photodissociation of ozone in the Hartley band: A theoretical analysis

Zhu

Grebenshchikov

et al. 2005

The Journal of Chemical Physics

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Three-dimensional diabatic potential energy surfaces for the lowest four electronic states of ozone with 1A' symmetry-termed X, A, B, and R-are constructed from electronic structure calculations. The diabatization is performed by reassigning corresponding energy points. Although approximate, these diabatic potential energy surfaces allow one to study the uv photodissociation of ozone on a level of theory not possible before. In the present work photoexcitation in the Hartley band and subsequent dissociation into the singlet channel, O3X+hnu-->O(1D)+O2(a 1Deltag), are investigated by means of quantum mechanical and classical trajectory calculations using the diabatic potential energy surface of the B state. The calculated low-resolution absorption spectrum as well as the vibrational and rotational state distributions of O2(a 1Deltag) are in good agreement with available experimental results.

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“…42 in Fig. (27) to calculate the intermediate distributions. The calculated spectrum stems mainly from the B state, agrees with experiment over a broad range of scattered photon wavelengths λ S , and quantita-tively reproduces the rapidly decreasing intensity with growing λ S , the multiplet structure of the emission, and the intensity patterns within multiplets.…”

Section: Intermediate Distributions From the Raman Emission Amplitudesmentioning

confidence: 99%

“…14,15,[27][28][29][30][31] The diagram in Fig. The two dissociation channels are spin-allowed and, combined, carry most of the reaction flux: 27,29 The two dissociation channels are spin-allowed and, combined, carry most of the reaction flux: 27,29 …”

mentioning

confidence: 99%

Intermediate photofragment distributions as probes of non-adiabatic dynamics at conical intersections: application to the Hartley band of ozone

Picconi

Grebenshchikov

2015

Phys. Chem. Chem. Phys.

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Quantum dynamics at a reactive two-state conical intersection lying outside the Franck-Condon zone is studied for a prototypical reaction of ultraviolet photodissociation of ozone in the Hartley band. The focus is on the vibrational distributions in the two electronic states at intermediate interfragment distances near the intersection. Such intermediate distributions of strongly interacting photofragments contain unique information on the location and shape of the conical intersection. Multidimensional Landau-Zener modeling provides a framework to reverse engineer the molecular geometry-dependent Massey parameter of the intersection from the intermediate distributions. The conceptual approach is demonstrated for the intermediate O-O bond stretch distributions which become strongly inverted on adiabatic passage through the intersection. It is further demonstrated that intermediate distributions can be reconstructed from the photoemission spectrum of the dissociating molecule. The illustration, given using quantum mechanical calculations of resonance Raman profiles for ozone, completes a practicable cycle of conversion of intermediate distributions into topographic features of the conical intersection.

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Photochemistry of Ozone: Surprises and Recent Lessons

Cited by 93 publications

References 9 publications

Nonadiabatic dynamics of O(1D) + N2$( {X{}^1\Sigma _g^ + } )\rightarrow $(XΣg+1)→O(3P) + N2$ ( {X{}^1\Sigma _g^ + } )$(XΣg+1) on three coupled potential surfaces: Symmetry, Coriolis, spin-orbit, and Renner-Teller effects

Nonadiabatic dynamics of O(1D) + N2$( {X{}^1\Sigma _g^ + } )\rightarrow $(XΣg+1)→O(3P) + N2$ ( {X{}^1\Sigma _g^ + } )$(XΣg+1) on three coupled potential surfaces: Symmetry, Coriolis, spin-orbit, and Renner-Teller effects

The photodissociation of ozone in the Hartley band: A theoretical analysis

Intermediate photofragment distributions as probes of non-adiabatic dynamics at conical intersections: application to the Hartley band of ozone

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