Nonadiabatic Quantum Dynamics Predissociation of H2O+(B̃ 2B2)

Suárez, Jaime; Méndez, L.; Rabadán, I.

doi:10.1021/jz5022894

Cited by 26 publications

(28 citation statements)

References 32 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…As a function of the angle, the potential energy surfaces of the resonant states show clear indications of conical intersections. Similar conical intersections are found among the potential energy surfaces of excited ionic states [25]. Since the resonant states are Rydberg states that converge to the excited ionic cores, the same behavior of the potentials are found for the resonant states.…”

Section: A Resonant States For Direct Drsupporting

confidence: 74%

Theoretical study of the mechanism ofH2O+dissociative recombination

et al. 2015

View full text Add to dashboard Cite

By combining electronic structure and scattering calculations, quasidiabatic potential energy surfaces of both bound Rydberg and electronic resonant states of the water molecule are calculated at the multi-reference configuration interaction level. The scattering matrix calculated at low collision energy is used to obtain explicitly all couplings elements responsible for the electronic capture to bound Rydberg states. These are used to estimate the cross section arising from the indirect mechanism of dissociative recombination. Additionally, the role of the direct capture and dissociation through the resonant states is explored using wave packet propagation along one-dimensional slices of the multi-dimensional potential energy surfaces.

show abstract

Section: A Resonant States For Direct Drsupporting

confidence: 74%

Theoretical study of the mechanism ofH2O+dissociative recombination

et al. 2015

View full text Add to dashboard Cite

show abstract

“…The product channels (1.1) and (1.2) are uncoupled within the adiabatic Born-Oppenheimer (BO) approximation and occur, respectively, on the two lowest X 2 A 00 and Ã 2 A 0 PESs of OH 2 + , which transform as 2 B 1 and 2 A 1 , respectively, in C 2v symmetry. 13. These two electronic states of H 2 O + correspond to the degenerate components of a 2 P u species, when the molecule is in a linear arrangement, and the associated nonadiabatic (NA) Renner-Teller (RT) effects can remarkably influence the dynamics of these collisions, as they also occur for the X 2 B 1 À Ã 2 A 1 optical spectrum 12 of H 2 + O.…”

Section: Introductionmentioning

confidence: 99%

Born–Oppenheimer and Renner–Teller coupled-channel quantum reaction dynamics of O(³P) + H₂⁺(X²Σ_g⁺) collisions

Gamallo

Defazio

González

et al. 2015

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

We present Born-Oppenheimer (BO) and Renner-Teller (RT) time dependent quantum dynamics studies of the reactions O((3)P) + H2(+)(X(2)Σg(+)) → OH(+)(X(3)Σ(-)) + H((2)S) and OH(X(2)Π) + H(+). We consider the OH2(+) X[combining tilde](2)A'' and Ã(2)A' electronic states that correlate with a linear (2)Π species. The electronic angular momenta operators L[combining circumflex] and L[combining circumflex](2) are considered in nonadiabatic coupled-channel calculations, where the associated RT effects are due to diagonal V(RT) potentials that add up to the PESs and to off-diagonal C(RT) couplings between the potential energy surfaces (PESs). Initial-state-resolved reaction probabilities PI, integral cross sections σI, and rate constants kI are obtained using recent ab initio PESs and couplings and the real wavepacket formalism. Because the PESs are strongly attractive, PI have no threshold energy and are large, σI decrease with collision energy, and kI depend little on the temperature. The X[combining tilde](2)A'' PES is up to three times more reactive than the Ã(2)A' PES and H2(+) rotational effects (j0 = 0, 1) are negligible. The diagonal V(RT) potentials are strongly repulsive at the collinearity and nearly halve all low-energy observables with respect to the BO ones. The off-diagonal C(RT) couplings are important at low partial waves, where they mix the X[combining tilde](2)A'' and Ã(2)A' states up to ∼20%. However, V(RT) effects predominate over the C(RT) ones that change at most by ∼19% the BO values of σI and kI. The reaction O((3)P) + H2(+)(X(2)Σg(+)) → OH(+)(X(3)Σ(-)) + H((2)S) is probably one of the most reactive atom + diatom collisions because its RT rate constant at room temperature is equal to 2.26 × 10(-10) cm(3) s(-1). Within the BO approximation, the present results agree rather well with recent quasiclassical and centrifugal-sudden data using the same PESs.

show abstract

“…1b 1 is the HOMO orbital, essentially a non-bonding 2p y orbital of the oxygen atom, perpendicular to the molecular plane, while the electron occupying the 1b 2 orbital is delocalized between the oxygen and hydrogen atoms, and its removal leads to the formation of H 2 O + (B 2 B 2 ), which readily predissociates following the mechanism recently described in Ref. [34].…”

Section: Resultsmentioning

confidence: 95%

“…To our knowledge, lattice methods have not been applied to ion-molecule collisions. Our treatment is based on the GridTDSE [33] parallel computational package that we have recently applied to study the predissociation of the water cation [34]. In addition to the calculation of electron transition probabilities, the numerical integration of the TDSE provides a direct visualization of the electronic dynamics.…”

Section: Introductionmentioning

confidence: 99%

Lattice description of electron loss in high-energy H++H2O collisions

et al. 2015

Self Cite

View full text Add to dashboard Cite

Esta es la versión de autor del artículo publicado en: This is an author produced version of a paper published in: AbstractElectron loss in proton-water collisions is studied in the energy range 100 keV < E < 1 MeV by employing a three-center model potential. The electron-loss probabilities are calculated by applying a new lattice method that yields cross sections which are in good agreement with previous semiclassical close-coupling and classical calculations. The lattice method also provides a straightforward visualization of the ionization mechanism at high impact velocities that involves a quasi-free expansion of the electron cloud.

show abstract

Nonadiabatic Quantum Dynamics Predissociation of H₂O⁺(B̃ ²B₂)

Cited by 26 publications

References 32 publications

Theoretical study of the mechanism ofH2O+dissociative recombination

Theoretical study of the mechanism ofH2O+dissociative recombination

Born–Oppenheimer and Renner–Teller coupled-channel quantum reaction dynamics of O(³P) + H₂⁺(X²Σ_g⁺) collisions

Lattice description of electron loss in high-energy H++H2O collisions

Contact Info

Product

Resources

About

Nonadiabatic Quantum Dynamics Predissociation of H2O+(B̃ 2B2)

Cited by 26 publications

References 32 publications

Theoretical study of the mechanism ofH2O+dissociative recombination

Theoretical study of the mechanism ofH2O+dissociative recombination

Born–Oppenheimer and Renner–Teller coupled-channel quantum reaction dynamics of O(3P) + H2+(X2Σg+) collisions

Lattice description of electron loss in high-energy H++H2O collisions

Contact Info

Product

Resources

About

Nonadiabatic Quantum Dynamics Predissociation of H₂O⁺(B̃ ²B₂)

Born–Oppenheimer and Renner–Teller coupled-channel quantum reaction dynamics of O(³P) + H₂⁺(X²Σ_g⁺) collisions