Photodissociation study of CO2 on the formation of state-correlated CO(X1Σ+, <i>v</i>) with O(3P2) photoproducts in the low energy band centered at 148 nm

Liu, Qian; Li, Zheng; Liu, Peng; Yang, Wenshao; Yang, Xueming; Yu, Shengrui

doi:10.1063/5.0139678

Cited by 3 publications

(1 citation statement)

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“…The experiment employed the time-sliced velocity-mapped ion imaging apparatus combined with two independent laser sources (a tunable VUV source for photolysis and a fixed UV source for (2 + 1) REMPI detection) for CO 2 molecular photodissociation. The detailed configuration of the experimental setup has been introduced in our previous studies, − and thus only a brief description is presented here. The CO 2 molecular beam (the rotational temperature was ∼10 K) was formed in a pulsed supersonic expansion of 10% CO 2 in Ar at a 1 bar backing pressure.…”

Section: Methodsmentioning

confidence: 99%

Wavelength-Dependent Dynamics of the O(¹D₂) Channel in the ¹Δ_u State Photodissociation of CO₂

Liu,

Tan,

Zou

et al. 2024

J. Phys. Chem. A

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The wavelength-dependent dynamics of the O( 1 D 2 ) channel, formed by photoexcitation of CO 2 to the 1 Δ u state at 143.53−153.03 nm, is investigated by using the time-sliced velocity-mapped ion imaging method. The measured ionic peaks of the O( 1 D 2 ) images are analyzed to determine the total kinetic energy release (TKER) spectra and image anisotropy parameters. The structures observed in the TKER spectra can be directly assigned to the ro-vibrational state distributions of the counter CO photofragments. Compared to those observed at 157 and 155 nm, the highly rotationally excited CO photofragments still obviously appear in v = 0 and 1, but the fraction of rotational excitations is significantly reduced. Conversely, the CO photofragments exhibit substantially higher vibrational excitations, implying that the nearly linear 2 1 A′ state also contributes to dissociation in addition to the bend configuration. The image anisotropy parameters display an extremely slow decreasing trend with an increase of the CO ro-vibrational state besides those for the highest ro-vibrationally excited CO photofragments. Nevertheless, the nonaxial recoil effect, suggested in previous photodissociation studies of CO 2 and other triatomic molecular systems, is still appropriate to explain the observations of internal energy dependences of image anisotropy parameters.

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Section: Methodsmentioning

confidence: 99%

Wavelength-Dependent Dynamics of the O(¹D₂) Channel in the ¹Δ_u State Photodissociation of CO₂

Liu,

Tan,

Zou

et al. 2024

J. Phys. Chem. A

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Resonance-state selective photodissociation dynamics of OCS + hv → CS(X1Σ+) + O(3Pj=2,1,0) via the 21Σ+ state

Liu

et al. 2023

The Journal of Chemical Physics

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Understanding vacuum ultraviolet photodissociation dynamics of Carbonyl sulfide (OCS) is of considerable importance in the study of atmospheric chemistry. Yet, photodissociation dynamics of the CS(X1Σ+) + O(3Pj=2,1,0) channels following excitation to the 21Σ+(ν1′,1,0) state has not been clearly understood so far. Here, we investigate the O(3Pj=2,1,0) elimination dissociation processes in the resonance-state selective photodissociation of OCS between 147.24 and 156.48 nm by using the time-sliced velocity-mapped ion imaging technique. The total kinetic energy release spectra are found to exhibit highly structured profiles, indicative of the formation of a broad range of vibrational states of CS(1Σ+). The fitted CS(1Σ+) vibrational state distributions differ for the three 3Pj spin–orbit states, but a general trend of the inverted characteristics is observed. Additionally, the wavelength-dependent behaviors are also observed in the vibrational populations for CS(1Σ+, v). The CS(X1Σ+, v = 0) has a significantly strong population at several shorter wavelengths, and the most populated CS(X1Σ+, v) is gradually transferred to a higher vibrational state with the decrease in the photolysis wavelength. The measured overall β-values for the three 3Pj spin–orbit channels slightly increase and then abruptly decrease as the photolysis wavelength increases, while the vibrational dependences of β-values show an irregularly decreasing trend with increasing CS(1Σ+) vibrational excitation at all studied photolysis wavelengths. The comparison of the experimental observations for this titled channel and the S(3Pj) channel reveals that two different intersystem crossing mechanisms may be involved in the formation of the CS(X1Σ+) + O(3Pj=2,1,0) photoproducts via the 21Σ+ state.

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Photodissociation of CO2 via the 1Πg state: Wavelength-dependent imaging studies of O(1D2) photoproducts

Liu,

Gao,

Liu

et al. 2024

The Journal of Chemical Physics

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Photodissociation of CO2 via the 1Πg state is investigated using a time-sliced velocity-mapped ion imaging apparatus combined with a tunable vacuum ultraviolet photolysis source. The main O(1D2) + CO(X1Σ+) channel is directly observed from the measured images of O(1D2) photoproducts at 129.08–134.76 nm. The total kinetic energy release spectra determined based on these images show that the energetic thresholds for the O(1D2) + CO(X1Σ+) photoproducts correspond to the thermochemical thresholds for the photodissociation of CO2(v2 = 0) and CO2(v2 = 1). One significant difference among the CO(X1Σ+, v) vibrational distributions for the predominant CO2(v2 = 0) dissociation is that the population of CO(v = 0) becomes favorable at 130.23–133.45 nm compared to the Boltzmann-like component (v > 0) that always exists at 129.08–134.76 nm. The wavelength dependences of the overall β are found to follow the variation trend of the CO(v = 0) abnormal intensity. The vibrational state-specific β values present a roughly decreasing trend with an increase in v, whereas β(v = 0) appears to be significantly larger than β(v = 1) at 130.23–133.45 nm compared to 134.76 and 129.08 nm. The non-statistical CO(v = 0) with larger β values at 130.23–133.45 nm implies that an additional pathway may open through the conical intersection coupling to the dissociative 21A′ state, except for the ever-existing pathway that yields the Boltzmann-like component. In contrast, at 129.08 nm, the restoration of the statistical equilibrium in the CO(X1Σ+, v) vibrational distribution may be caused by the emergence of novel dissociation pathways arising from the participation of the 31A″ state.

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Photodissociation study of CO2 on the formation of state-correlated CO(X1Σ+, v) with O(3P2) photoproducts in the low energy band centered at 148 nm

Cited by 3 publications

References 32 publications

Wavelength-Dependent Dynamics of the O(¹D₂) Channel in the ¹Δ_u State Photodissociation of CO₂

Wavelength-Dependent Dynamics of the O(¹D₂) Channel in the ¹Δ_u State Photodissociation of CO₂

Resonance-state selective photodissociation dynamics of OCS + hv → CS(X1Σ+) + O(3Pj=2,1,0) via the 21Σ+ state

Photodissociation of CO2 via the 1Πg state: Wavelength-dependent imaging studies of O(1D2) photoproducts

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Photodissociation study of CO2 on the formation of state-correlated CO(X1Σ+, v) with O(3P2) photoproducts in the low energy band centered at 148 nm

Cited by 3 publications

References 32 publications

Wavelength-Dependent Dynamics of the O(1D2) Channel in the 1Δu State Photodissociation of CO2

Wavelength-Dependent Dynamics of the O(1D2) Channel in the 1Δu State Photodissociation of CO2

Resonance-state selective photodissociation dynamics of OCS + hv → CS(X1Σ+) + O(3Pj=2,1,0) via the 21Σ+ state

Photodissociation of CO2 via the 1Πg state: Wavelength-dependent imaging studies of O(1D2) photoproducts

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Wavelength-Dependent Dynamics of the O(¹D₂) Channel in the ¹Δ_u State Photodissociation of CO₂

Wavelength-Dependent Dynamics of the O(¹D₂) Channel in the ¹Δ_u State Photodissociation of CO₂