Rate constants for collision-induced emission of O2(a1Δg) with He, Ne, Ar, Kr, N2, CO2 and SF6 as collisional partners

Literature Information

Publication Date 2018-11-15
DOI 10.1039/C8CP06231E
Impact Factor 3.676
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Abstract

Rate constants for singlet oxygen collision induced emission of the a1Δg–X3Σ−g transition at 1.27 μm were measured for CO2, N2, SF6, and rare gases as collisional partners. Photolysis of ozone by 266 nm laser radiation produced singlet oxygen. We performed direct measurements of pressure dependences of the 1.27 μm emission intensity for partner gases. The measured rate constants kMa–X in the units of 10−24 cm3 s−1 are as follows: CO2 – 10 ± 2; N2 – 3.2 ± 0.6; SF6 – 7 ± 1; He – 1.1 ± 0.3; Ne – 1.3 ± 0.3; Ar – 2.8 ± 0.6; Kr – 6 ± 1. The measured values of kMa–X are close to the values calculated from absorption measurements. Considering the known rate constants kMb–a for the b1Σg+–a1Δg transition in the gas phase we found that the ratio kMa–X/kMb–a was constant and independent of a collisional partner according to the “spin–orbit based” mechanism of intensity borrowing proposed by Minaev (THEOCHEM, 1989, 183, 207). However, this ratio amounted to (1.3 ± 0.2) × 10−4, which is considerably lower than the theoretically predicted value of (3–6) × 10−4.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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