Nonadiabatic dynamics of O({sup 1}D) + N{sub 2}(X{sup 1}{Sigma}{sub g}{sup +}){yields}O({sup 3}P) + N{sub 2}(X{sup 1}{Sigma}{sub g}{sup +}) on three coupled potential surfaces: Symmetry, Coriolis, spin-orbit, and Renner-Teller effects

Journal Article · Tue Feb 07 00:00:00 EST 2012 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.3682467· OSTI ID:22047167

Defazio, Paolo ^[1]; Gamallo, Pablo ^[2]; Petrongolo, Carlo ^[3]

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1. Dipartimento di Chimica, Universita di Siena, Via A. Moro 2, I-53100 Siena (Italy)
2. Departament de Quimica Fisica i IQTC-UB, Universitat de Barcelona, C/Marti i Franques 1, 08028, Barcelona (Spain)
3. Istituto per i Processi Chimico-Fisici, Consiglio Nazionale delle Ricerche, Via G. Moruzzi 1, I-56124 Pisa (Italy)

We present the spin-orbit (SO) and Renner-Teller (RT) quantum dynamics of the spin-forbidden quenching O({sup 1}D) + N{sub 2}(X{sup 1}{Sigma}{sub g}{sup +}){yields}O({sup 3}P) + N{sub 2}(X{sup 1}{Sigma}{sub g}{sup +}) on the N{sub 2}O X-tilde{sup 1}A{sup '}, a-tilde{sup 3}A', and b-tilde{sup 3}A{sup '} coupled PESs. We use the permutation-inversion symmetry, propagate coupled-channel (CC) real wavepackets, and compute initial-state-resolved probabilities and cross sections {sigma}{sub j0} for the ground vibrational and the first two rotational states of N{sub 2}, j{sub 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 a-tilde{sup 3}A' is uncoupled in the centrifugal-sudden (CS) approximation at j{sub 0}= 0. The dynamics is resonance-dominated, the probabilities are larger at low K, {sigma}{sub j0} decrease with the collision energy and increase with j{sub 0}, and the CS {sigma}{sub 0} is lower than the CC one. The nonadiabatic interactions play different roles on the quenching dynamics, because the X-tilde{sup 1}A{sup '}-b-tilde{sup 3}A{sup '} SO effects are those most important while the a-tilde{sup 3}A'-b-tilde{sup 3}A{sup '} RT ones are negligible.

• OSTI ID: 22047167
• Journal Information: Journal of Chemical Physics, Vol. 136, Issue 5; Other Information: (c) 2012 American Institute of Physics; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

74 ATOMIC AND MOLECULAR PHYSICS
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ATOM-MOLECULE COLLISIONS
CORIOLIS FORCE
COUPLED CHANNEL THEORY
CROSS SECTIONS
DISSOCIATION
GROUND STATES
INTERACTIONS
L-S COUPLING
NITROUS OXIDE
PHOTOLYSIS
POTENTIAL ENERGY
PROBABILITY
QUENCHING
ROTATIONAL STATES
SPIN
SURFACES
VIBRATIONAL STATES