Formic acid chemiluminescence from cryogenic reaction between triplet methylene and oxygen

Yuan-Pern Lee; George C. Pimentel

doi:10.1063/1.441737

Formic acid chemiluminescence from cryogenic reaction between triplet methylene and oxygen

Yuan-Pern Lee^*, George C. Pimentel

^*Corresponding author for this work

Department of Applied Chemistry

Research output: Contribution to journal › Article › peer-review

22 Scopus citations

Abstract

Matrix samples of CH₂N₂/O₂/Ar were photolyzed at 8 °K. Subsequent slow warming produced the previously observed O₂ A′ ³Δ_u→X ³Σ_g^- thermoluminescence and two new progressions, one at 3100-3600 Å and one at 3900-4900 Å. With ¹⁸O₂, the 3100-3600 Å progression displayed isotopic shifts that allow two possible υ″ vibrational assignments to give ν₀₀=34 730 or 33 340 (±40) cm^-1 and ω_e″=1390±15 cm^-1. Similarly, the ¹⁸O₂ shifts in the 3900-4900 Å progression lead to two possible υ″ assignments to give ν₀₀=26 230 or 25 100 (±60) cm^-1 and ω_e″=1124±40 cm^-1. These spectroscopic parameters point to assignments of the a ³A″→X ¹A′ and A′ ¹A′→A ¹A″ transitions of HCOOH for the 3100-3600 and 3900-4900 Å progressions, respectively. These are the first observations of such transitions of formic acid and are attributed to the CH₂(³B₁)+O₂(³Σ _g^-) reaction in the cryogenic matrix.

Original language	English
Pages (from-to)	4851-4857
Number of pages	7
Journal	The Journal of chemical physics
Volume	74
Issue number	9
DOIs	https://doi.org/10.1063/1.441737
State	Published - 1 May 1981

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title = "Formic acid chemiluminescence from cryogenic reaction between triplet methylene and oxygen",

abstract = "Matrix samples of CH2N2/O2/Ar were photolyzed at 8 °K. Subsequent slow warming produced the previously observed O2 A′ 3Δu→X 3Σg- thermoluminescence and two new progressions, one at 3100-3600 {\AA} and one at 3900-4900 {\AA}. With 18O2, the 3100-3600 {\AA} progression displayed isotopic shifts that allow two possible υ″ vibrational assignments to give ν00=34 730 or 33 340 (±40) cm-1 and ωe″=1390±15 cm-1. Similarly, the 18O2 shifts in the 3900-4900 {\AA} progression lead to two possible υ″ assignments to give ν00=26 230 or 25 100 (±60) cm-1 and ωe″=1124±40 cm-1. These spectroscopic parameters point to assignments of the a 3A″→X 1A′ and A′ 1A′→A 1A″ transitions of HCOOH for the 3100-3600 and 3900-4900 {\AA} progressions, respectively. These are the first observations of such transitions of formic acid and are attributed to the CH2(3B1)+O2(3Σ g-) reaction in the cryogenic matrix.",

author = "Yuan-Pern Lee and Pimentel, {George C.}",

year = "1981",

month = may,

day = "1",

doi = "10.1063/1.441737",

language = "English",

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pages = "4851--4857",

journal = "The Journal of chemical physics",

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T1 - Formic acid chemiluminescence from cryogenic reaction between triplet methylene and oxygen

AU - Lee, Yuan-Pern

AU - Pimentel, George C.

PY - 1981/5/1

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N2 - Matrix samples of CH2N2/O2/Ar were photolyzed at 8 °K. Subsequent slow warming produced the previously observed O2 A′ 3Δu→X 3Σg- thermoluminescence and two new progressions, one at 3100-3600 Å and one at 3900-4900 Å. With 18O2, the 3100-3600 Å progression displayed isotopic shifts that allow two possible υ″ vibrational assignments to give ν00=34 730 or 33 340 (±40) cm-1 and ωe″=1390±15 cm-1. Similarly, the 18O2 shifts in the 3900-4900 Å progression lead to two possible υ″ assignments to give ν00=26 230 or 25 100 (±60) cm-1 and ωe″=1124±40 cm-1. These spectroscopic parameters point to assignments of the a 3A″→X 1A′ and A′ 1A′→A 1A″ transitions of HCOOH for the 3100-3600 and 3900-4900 Å progressions, respectively. These are the first observations of such transitions of formic acid and are attributed to the CH2(3B1)+O2(3Σ g-) reaction in the cryogenic matrix.

AB - Matrix samples of CH2N2/O2/Ar were photolyzed at 8 °K. Subsequent slow warming produced the previously observed O2 A′ 3Δu→X 3Σg- thermoluminescence and two new progressions, one at 3100-3600 Å and one at 3900-4900 Å. With 18O2, the 3100-3600 Å progression displayed isotopic shifts that allow two possible υ″ vibrational assignments to give ν00=34 730 or 33 340 (±40) cm-1 and ωe″=1390±15 cm-1. Similarly, the 18O2 shifts in the 3900-4900 Å progression lead to two possible υ″ assignments to give ν00=26 230 or 25 100 (±60) cm-1 and ωe″=1124±40 cm-1. These spectroscopic parameters point to assignments of the a 3A″→X 1A′ and A′ 1A′→A 1A″ transitions of HCOOH for the 3100-3600 and 3900-4900 Å progressions, respectively. These are the first observations of such transitions of formic acid and are attributed to the CH2(3B1)+O2(3Σ g-) reaction in the cryogenic matrix.

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DO - 10.1063/1.441737

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Formic acid chemiluminescence from cryogenic reaction between triplet methylene and oxygen

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