The interaction potential of NO-H2 in ground and A Rydberg state

Pajón-Suárez, Pedro; Valentín-Rodríguez, Mónica A.; Hernández‐Lamoneda, Ramón

doi:10.1016/j.cplett.2016.06.042

Cited by 8 publications

(6 citation statements)

References 28 publications

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“…Figures S1–S9 in the Supporting Information present similar PESs for NO and H 2 at other orientations; all of these PESs are purely repulsive on D 2 over the range of intermolecular distances considered and do not exhibit any evidence of conical intersections that can facilitate electronic quenching. The D 2 ( A 2 Σ + ) PESs developed by Hernández-Lamoneda and co-workers are similarly repulsive for intermolecular distances below 6 Å; the ON + H 2 collision complex they identified on D 2 is bound by only 13 cm –1 and has an intermolecular distance of 6.5 Å …”

Section: Resultsmentioning

confidence: 92%

“…Furthermore, the experimental results indicated a deviation in the angular momentum polarization moments from predictions for higher NO ( A 2 Σ + , N ′) states. Pajón-Suárez and co-workers reported an interaction PES for NO ( A 2 Σ + ) + H 2 over intermolecular distances ranging from 5–10 Å and found it comparable to the interaction PESs for NO ( A 2 Σ + ) and rare gas atoms . Pajón-Suárez further demonstrated that the linear NO–H 2 geometries in the ground state have a deeper well (∼50 cm –1 ) compared with the excited state (∼10 cm –1 ).…”

Section: Introductionmentioning

confidence: 78%

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Stereodynamic Control of Collision-Induced Nonadiabatic Dynamics of NO (A²Σ⁺) with H₂, N₂, and CO: Intermolecular Interactions Drive Collision Outcomes

et al. 2021

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Intermolecular interactions, stereodynamics, and coupled potential energy surfaces (PESs) all play a significant role in determining the outcomes of molecular collisions. A detailed knowledge of such processes is often essential for a proper interpretation of spectroscopic observations. For example, nitric oxide (NO), an important radical in combustion and atmospheric chemistry, is commonly quantified using laser-induced fluorescence on the A 2 Σ + ← X 2 Π transition band. However, the electronic quenching of NO (A 2 Σ + ) with other molecular species provides alternative nonradiative pathways that compete with fluorescence. While the cross sections and rate constants of NO (A 2 Σ + ) electronic quenching have been experimentally measured for a number of important molecular collision partners, the underlying photochemical mechanisms responsible for the electronic quenching are not well understood. In this paper, we describe the development of high-quality PESs that provide new physical insights into the intermolecular interactions and conical intersections that facilitate the branching between the electronic quenching and scattering of NO (A 2 Σ + ) with H 2 , N 2 , and CO. The PESs are calculated at the EOM-EA-CCSD/d-aug-cc-pVTZ//EOM-EA-CCSD/aug-cc-pVDZ level of theory, an approach that ensures a balanced treatment of the valence and Rydberg electronic states and an accurate description of the open-shell character of NO. Our PESs show that H 2 is incapable of electronically quenching NO (A 2 Σ + ) at low collision energies; instead, the two molecules will likely undergo scattering. The PESs of NO (A 2 Σ + ) with N 2 and CO are highly anisotropic and demonstrate evidence of electron transfer from NO (A 2 Σ + ) into the lowest unoccupied molecular orbital of the collision partner, that is, the harpoon mechanism. In the case of ON + CO, the PES becomes strongly attractive at longer intermolecular distances and funnels population to a conical intersection between NO (A 2 Σ + ) + CO and NO (X 2 Π) + CO. In contrast, for ON + N 2 , the conical intersection is preceded by an ∼0.40 eV barrier. Overall, our work shines new light into the impact of coupled PESs on the nonadiabatic dynamics of open-shell systems.

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Section: Resultsmentioning

confidence: 92%

Section: Introductionmentioning

confidence: 78%

Stereodynamic Control of Collision-Induced Nonadiabatic Dynamics of NO (A²Σ⁺) with H₂, N₂, and CO: Intermolecular Interactions Drive Collision Outcomes

et al. 2021

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“…Due to the larger size of D 2 , the differences in angular spacing between individual diffraction peaks were observed . Theoretically, two NO–H 2 PESs have been reported in the literature recently. , …”

Section: Introductionmentioning

confidence: 99%

State-to-State Differential Cross Sections for Inelastic Collisions of NO Radicals with para-H₂ and ortho-D₂

Zhi¹,

Vogels²,

Besemer³

et al. 2017

J. Phys. Chem. A

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We present state-to-state differential cross sections for collisions of NO molecules (X2Π1/2, j = 1/2f) with para-H2 and ortho-D2 molecules, at a collision energy of 510 and 450 cm–1, respectively. The angular scattering distributions for various final states of the NO radical are measured with high resolution using a crossed molecular beam apparatus that employs the combination of Stark deceleration and velocity map imaging. Rotational rainbows as well as diffraction oscillations are fully resolved in the scattering images. The observed angular scattering distributions are in excellent agreement with the cross sections obtained from quantum close-coupling scattering calculations based on recently computed NO–H2 potential energy surfaces, except for excitation of NO into the j = 7/2f channel. For this particular inelastic channel, a significant discrepancy with theory is observed, despite various additional measurements and calculations, at present, not understood.

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“…In general, experimentally obtained ICSs and DCSs for NO-H 2 inelastic collisions are in good agreement with the calculated cross sections based on ab initio NO-H 2 PESs. 22,23 Several experiments were performed to study collisions of NO with the molecular collision partners N 2 and O 2 as well. 24,25 The resolution in this type of experiments can be significantly enhanced using the Stark deceleration technique, which has also been recently applied to studies of bimolecular scattering.…”

Section: Introductionmentioning

confidence: 99%

Correlations in rotational energy transfer for NO–D2 inelastic collisions

Tang¹,

Besemer²,

Jongh³

et al. 2020

The Journal of Chemical Physics

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We present a combined experimental and theoretical study of state-to-state inelastic collisions between NO (X 2 Π 1/2 , j = 1/2, f ) radicals and D 2 (j = 0, 1, 2, 3) molecules at collision energies of 100 cm −1 and 750 cm −1 . Using the combination of Stark deceleration and velocity map imaging, we fully resolve pair-correlated excitations in the scattered molecules. Both spin-orbit conserving and spin-orbit changing transitions in the NO radical are measured, while the coincident rotational excitation (j = 0 → j = 2) and rotational de-excitation (j = 2 → j = 0 and j = 3 → j = 1) in D 2 are observed. De-excitation of D 2 shows a strong dependence on the spin-orbit excitation of NO. We observe translationto-rotation energy transfer as well as direct rotation-to-rotation energy transfer at the lowest collision energy probed. The experimental results are in good agreement with cross sections obtained from quantum coupled-channels calculations based on recent NO-D 2 potential energy surfaces. The observed trends in the correlated scattering cross sections are understood in terms of the NO-D 2 quadrupole-quadrupole interaction.

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The interaction potential of NO-H2 in ground and A Rydberg state

Cited by 8 publications

References 28 publications

Stereodynamic Control of Collision-Induced Nonadiabatic Dynamics of NO (A²Σ⁺) with H₂, N₂, and CO: Intermolecular Interactions Drive Collision Outcomes

Stereodynamic Control of Collision-Induced Nonadiabatic Dynamics of NO (A²Σ⁺) with H₂, N₂, and CO: Intermolecular Interactions Drive Collision Outcomes

State-to-State Differential Cross Sections for Inelastic Collisions of NO Radicals with para-H₂ and ortho-D₂

Correlations in rotational energy transfer for NO–D2 inelastic collisions

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The interaction potential of NO-H2 in ground and A Rydberg state

Cited by 8 publications

References 28 publications

Stereodynamic Control of Collision-Induced Nonadiabatic Dynamics of NO (A2Σ+) with H2, N2, and CO: Intermolecular Interactions Drive Collision Outcomes

Stereodynamic Control of Collision-Induced Nonadiabatic Dynamics of NO (A2Σ+) with H2, N2, and CO: Intermolecular Interactions Drive Collision Outcomes

State-to-State Differential Cross Sections for Inelastic Collisions of NO Radicals with para-H2 and ortho-D2

Correlations in rotational energy transfer for NO–D2 inelastic collisions

Contact Info

Product

Resources

About

Stereodynamic Control of Collision-Induced Nonadiabatic Dynamics of NO (A²Σ⁺) with H₂, N₂, and CO: Intermolecular Interactions Drive Collision Outcomes

Stereodynamic Control of Collision-Induced Nonadiabatic Dynamics of NO (A²Σ⁺) with H₂, N₂, and CO: Intermolecular Interactions Drive Collision Outcomes

State-to-State Differential Cross Sections for Inelastic Collisions of NO Radicals with para-H₂ and ortho-D₂