Laser-induced fluorescence of PO-photofragments of dimethyl
methylphosphonate

Sergei M. Bobrovnikov; Sergei M. Bobrovnikov; Evgeny V. Gorlov; Evgeny V. Gorlov; Viktor I. Zharkov

doi:10.1364/AO.456005

Applied Optics
Vol. 61,
Issue 21,
pp. 6322-6329
(2022)
•https://doi.org/10.1364/AO.456005

Laser-induced fluorescence ofPO-photofragments of dimethyl methylphosphonate

Sergei M. Bobrovnikov, Evgeny V. Gorlov, and Viktor I. Zharkov

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Sergei M. Bobrovnikov, Evgeny V. Gorlov, and Viktor I. Zharkov, "Laser-induced fluorescence of PO-photofragments of dimethyl methylphosphonate," Appl. Opt. 61, 6322-6329 (2022)

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Abstract

The paper presents the results of calculating the absorption spectrum of a phosphorus monoxide (PO) molecule corresponding to the ${A^2}{\Sigma ^ +}(v^\prime = {{0}})-{X^2}\Pi ({v^{{\prime \prime}}} = {{0}})$ transition. The efficiency of excitation of the PO molecule is estimated as a function of the spectral parameters of the laser radiation. The positions of the fluorescence bands of PO are calculated. It is shown that the use of excitation wavelengths near the bandheads of the (${P_{22}} + {Q_{12}}$) and ${P_{12}}$ branches of the ${A^2}{\Sigma ^ +}(v^\prime = {{0}}) - {X^2}{\Pi _{3/2}}({v^{{\prime \prime}}} = {{0}})$ band provides spectral separation of the (0, 1) $\gamma$-band of the LIF of PO and vibrational-rotational Raman spectrum of atmospheric oxygen. The spectral responses of dimethyl methylphosphonate vapor in air under the action of KrF-laser radiation at a wavelength of 247.78 nm have been experimentally studied. In the wavelength range 252–260 nm, the (0, 1) $\gamma$-band of the LIF of PO-fragments and the vibrational-rotational band of spontaneous Raman scattering on oxygen molecules are unambiguously interpreted. It is shown that the results of calculations of the shape and position of the fluorescence spectra are in good agreement with the experimental data.

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Data availability

NIST’s Atomic Spectra database can be found in Ref. [30]. All other data underlying the results presented in this paper are available from the authors upon reasonable request.

30. A. Kramida, Y. Ralchenko, J. Reader, and the NIST ASD Team, “Atomic spectra database,” Ver. 5.9, NIST, 2021, https://doi.org/10.18434/T4W30F.

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No	Reaction
Primary processes
1a	$D M M P (o r {D M M P}^{+}) + n h ν \to P O (X, ν^{''}), P (^{4} S), P (^{2} D), P (^{2} P) + X$ ; $X = C H_{2}, H_{2}, C O, {C H}_{3} O H, \dots$
1b	$\to {D M M P}^{+}$ ;
1c	$\to D M M P - i s o m e r s (o r D M M P^{+} - i s o m e r s)$ ;
1 d	$\to {D M M P}^{} (o r {[{D M M P}^{+}]}^{}) \to D M M P (o r {D M M P}^{+})$ ;
Secondary processes
2	$P (^{4} S) + O_{2} \to P O + O;$
3a	$P (^{2} D) + O_{2} \to P O + O;$
3b	$\to P (^{4} S) + O_{2}$ ;
4a	$P (^{2} D) + {C O}_{2} \to P O + C O$ ;
4b	$\to P (^{4} S) + {C O}_{2}$ ;
5	$P (^{2} D) + N_{2} \to P (^{4} S) + N_{2};$
6a	$P (^{2} P) + O_{2} \to P O + O;$
6b	$\to P (^{2} D) + O_{2}$ ;
6c	$\to P (^{4} S) + O_{2}$ ;
7a	$P (^{2} P) + {C O}_{2} \to P O + C O;$
7b	$\to P (^{2} D) + {C O}_{2}$ ;
7c	$\to P (^{4} S) + {C O}_{2}$ ;
8a	$P (^{2} P) + N_{2} \to P (^{2} D) + N_{2};$
8b	$\to P (^{4} S) + N_{2}$ ;

		$J^{''}$	Fraction of PO-Fragments
Head Forming Branch	$λ_{0}^{max}$ (nm, air)	$Δ λ = 5 p m$
$A^{2} Σ^{+} - X^{2} Π_{1 / 2}$ band
$Q_{11} + P_{21}$	246.261	3.5–10.5 ( $Q_{11}$ ) 3.5–10.5 ( $P_{21}$ )	0.054
$P_{11}$	246.399	19.5–26.5	0.014
$A^{2} Σ^{+} - X^{2} Π_{3 / 2}$ band
$P_{22} + Q_{12}$	247.621	4.5–11.5 ( $P_{22}$ ) 4.5–9.5 ( $Q_{12}$ )	0.016
$P_{12}$	247.776	21.5–30.5	0.004

Parameter	Value
Wavelength, nm	$247.776 \pm 0.003$
Tuning range, nm	247.60–249.50
Maximum pulse energy, mJ	100
Emission linewidth, pm	5
Pulse repetition rate, Hz	1–10
Pulse duration, ns	30
Beam divergence, mrad	1
Output beam cross section, ${m m}^{2}$	$18 \times 9$
Polarization degree	0.99

No	Reaction
Primary processes
1a	$D M M P (o r {D M M P}^{+}) + n h ν \to P O (X, ν^{''}), P (^{4} S), P (^{2} D), P (^{2} P) + X$ ; $X = C H_{2}, H_{2}, C O, {C H}_{3} O H, \dots$
1b	$\to {D M M P}^{+}$ ;
1c	$\to D M M P - i s o m e r s (o r D M M P^{+} - i s o m e r s)$ ;
1 d	$\to {D M M P}^{} (o r {[{D M M P}^{+}]}^{}) \to D M M P (o r {D M M P}^{+})$ ;
Secondary processes
2	$P (^{4} S) + O_{2} \to P O + O;$
3a	$P (^{2} D) + O_{2} \to P O + O;$
3b	$\to P (^{4} S) + O_{2}$ ;
4a	$P (^{2} D) + {C O}_{2} \to P O + C O$ ;
4b	$\to P (^{4} S) + {C O}_{2}$ ;
5	$P (^{2} D) + N_{2} \to P (^{4} S) + N_{2};$
6a	$P (^{2} P) + O_{2} \to P O + O;$
6b	$\to P (^{2} D) + O_{2}$ ;
6c	$\to P (^{4} S) + O_{2}$ ;
7a	$P (^{2} P) + {C O}_{2} \to P O + C O;$
7b	$\to P (^{2} D) + {C O}_{2}$ ;
7c	$\to P (^{4} S) + {C O}_{2}$ ;
8a	$P (^{2} P) + N_{2} \to P (^{2} D) + N_{2};$
8b	$\to P (^{4} S) + N_{2}$ ;

		$J^{''}$	Fraction of PO-Fragments
Head Forming Branch	$λ_{0}^{max}$ (nm, air)	$Δ λ = 5 p m$
$A^{2} Σ^{+} - X^{2} Π_{1 / 2}$ band
$Q_{11} + P_{21}$	246.261	3.5–10.5 ( $Q_{11}$ ) 3.5–10.5 ( $P_{21}$ )	0.054
$P_{11}$	246.399	19.5–26.5	0.014
$A^{2} Σ^{+} - X^{2} Π_{3 / 2}$ band
$P_{22} + Q_{12}$	247.621	4.5–11.5 ( $P_{22}$ ) 4.5–9.5 ( $Q_{12}$ )	0.016
$P_{12}$	247.776	21.5–30.5	0.004

Abstract

Data availability

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Figures (11)

Tables (3)

Equations (1)

Applied Optics