Collision-induced emission of singlet oxygen in the visible spectral region at temperatures of 90–315 K

Загидуллин, М. В.; Svistun, M I; Khvatov, N A; Insapov, A. S.

doi:10.1134/s0030400x14040262

Cited by 4 publications

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“…The concentration of O 2 (a) molecules can also be determined by the intensity of CIE (dimole emission) in the visible spectral region, O 2 (a) + O 2 (a) → О 2 (X) + О 2 (X) + hν (λ = 634 nm), (4) O 2 (a) + O 2 (a) → О 2 (X) + О 2 (X, 1) + hν (λ = 703 nm), (5) where О 2 (X) and О 2 (X, 1) are the oxygen molecules in ground electronic state 3 Σ at vibrational levels ν = 0 and ν = 1, respectively. The intensity of CIE (4), (5) does not depend on the concentration of other gas mixture components, but depends on temperature [13,14].…”

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confidence: 99%

1.27-μm emission of O2(1Δ) induced by collisions with oxygen molecules

2015

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The intensities of collision-induced emission of singlet oxygen O 2 (a 1 Δ) caused by the following two radiative processes-O 2 (a, ν = 0) + O 2 (a, ν = 0) → O 2 (X, ν = 0) + О 2 (X, ν = 0, 1) + hν and O 2 (a, ν = 0) + O 2 → O 2 (X, ν = 0) + O 2 + hν-are studied by emission spectroscopy. It is found that the rate constants of these radiative processes are (1.54 ± 0.23) × 10 -22 cm 3 s -1 and (2.74 ± 0.4) × 10 -23 cm 3 s -1 , respectively.

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Section: Introductionmentioning

confidence: 99%

1.27-μm emission of O2(1Δ) induced by collisions with oxygen molecules

2015

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“…The red light emitted by singlet molecular oxygen is a standard textbook example of chemiluminescence, , and has a long history of experimental − and theoretical ,− investigations. The energy of the strongest band of the emitted light is approximately twice as large as that of the vertical O 2 ( a 1 Δ g ) → O 2 ( X 3 ∑ g – ) transition, which is spin-forbidden.…”

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“…The energy of the strongest band of the emitted light is approximately twice as large as that of the vertical O 2 ( a 1 Δ g ) → O 2 ( X 3 ∑ g – ) transition, which is spin-forbidden. The intensity of the emission depends quadratically on the concentration of singlet excited oxygen, and the process therefore has been assigned to a simultaneous (“dimol”) transition of two singlet oxygen molecules into the singlet ground state of the complex, followed by its dissociation into two triplet oxygen molecules: ,,,, …”

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“…Since the emission starts from short-lived excited species and requires the intermolecular interaction of two systems in which the corresponding transitions are forbidden individually, the signal is very weak and relatively hard to study experimentally. , The spectral characteristics, the band position and shape, along with their temperature dependence, were recorded long time ago, ,, while the corresponding rate constantswhich also require the determination of the concentration of the transient O 2 ( a 1 Δ g )were reported recently by Zagidullin et al , The theoretical investigations performed so far mostly concerned the potential energy surfaces of the electronic states − that determine the geometry and binding energy of the dimer complex. These studies showed that the O 2 –O 2 intermolecular potential is predominantly repulsive, and shows only a shallow van der Waals minimum at large intermolecular separation with very small binding energy …”

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“…The numerical values of the emission rate constants simulated using eq are summarized and compared to the experiment of Zagidullin et al , in Table . In agreement with the simulated intensities, the predicted rate constants also show a large variation with the orientation, giving, in certain cases, zero value due to symmetry.…”

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Dimol Emission of Oxygen Made Possible by Repulsive Interaction

Tajti

Lendvay

Szalay

2017

J. Phys. Chem. Lett.

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For the energy emitted in a textbook example of chemiluminescence, the peculiar red light produced by singlet molecular oxygen is about twice that of the spin-forbidden O(aΔ) → O(X∑) transition. Theoretical studies suggest that the O(aΔ)-O(aΔ) van der Waals interaction is weak, and at room temperature no long-lived complex is formed. Our high-level ab initio calculations show that in the bound domain of the dimer, the oscillator strength is very small, but increases at smaller intermolecular separations, where, however, the interaction is repulsive. We propose that the emission is induced by collisions: it takes place "on-the-fly", when the collision energy allows the system to access the repulsive part of the potential energy surface where the oscillator strength is relatively large. The contribution of different orientations of the two O molecules to the emission has been evaluated with a simple semiclassical model. The position of the emission peak is in accord with the experiment, and the estimated rate coefficient of collision-induced emission averaged over orientation is in reasonable agreement with the measurements.

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Luminescence of the (O₂(a¹Δ_g))₂ collisional complex in the temperature range of 90-315 K: Experiment and theory

Загидуллин

Pershin

Azyazov

et al. 2015

The Journal of Chemical Physics

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Experimental and theoretical studies of collision induced emission of singlet oxygen molecules O2(a(1)Δg) in the visible range have been performed. The rate constants, half-widths, and position of peaks for the emission bands of the (O2(a(1)Δg))2 collisional complex centered around 634 nm (2) and 703 nm (3) have been measured in the temperature range of 90-315 K using a flow-tube apparatus that utilized a gas-liquid chemical singlet oxygen generator. The absolute values of the spontaneous emission rate constants k2 and k3 are found to be similar, with the k3/k2 ratio monotonically decreasing from 1.1 at 300 K to 0.96 at 90 K. k2 slowly decreases with decreasing temperature but a sharp increase in its values is measured below 100 K. The experimental results were rationalized in terms of ab initio calculations of the ground and excited potential energy and transition dipole moment surfaces of singlet electronic states of the (O2)2 dimole, which were utilized to compute rate constants k2 and k3 within a statistical model. The best theoretical results reproduced experimental rate constants with the accuracy of under 40% and correctly described the observed temperature dependence. The main contribution to emission process (2), which does not involve vibrational excitation of O2 molecules at the ground electronic level, comes from the spin- and symmetry-allowed 1(1)Ag←(1)B3u transition in the rectangular H configuration of the dimole. Alternatively, emission process (3), in which one of the monomers becomes vibrationally excited in the ground electronic state, is found to be predominantly due to the vibronically allowed 1(1)Ag←2(1)Ag transition induced by the asymmetric O-O stretch vibration in the collisional complex. The strong vibronic coupling between nearly degenerate excited singlet states of the dimole makes the intensities of vibronically and symmetry-allowed transitions comparable and hence the rate constants k2 and k3 close to one another.

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Collision-induced emission of singlet oxygen in the visible spectral region at temperatures of 90–315 K

Cited by 4 publications

References 35 publications

1.27-μm emission of O2(1Δ) induced by collisions with oxygen molecules

1.27-μm emission of O2(1Δ) induced by collisions with oxygen molecules

Dimol Emission of Oxygen Made Possible by Repulsive Interaction

Luminescence of the (O₂(a¹Δ_g))₂ collisional complex in the temperature range of 90-315 K: Experiment and theory

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Collision-induced emission of singlet oxygen in the visible spectral region at temperatures of 90–315 K

Cited by 4 publications

References 35 publications

1.27-μm emission of O2(1Δ) induced by collisions with oxygen molecules

1.27-μm emission of O2(1Δ) induced by collisions with oxygen molecules

Dimol Emission of Oxygen Made Possible by Repulsive Interaction

Luminescence of the (O2(a1Δg))2 collisional complex in the temperature range of 90-315 K: Experiment and theory

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Luminescence of the (O₂(a¹Δ_g))₂ collisional complex in the temperature range of 90-315 K: Experiment and theory