TY - JOUR
T1 - Limonene
T2 - A scented and versatile tropospheric free radical deactivator
AU - Francisco-Márquez, Misaela
AU - Galano, Annia
N1 - Publisher Copyright:
© 2023 Wiley Periodicals LLC.
PY - 2023/12/15
Y1 - 2023/12/15
N2 - The reactions of limonene with various free radicals (•OCH3, •OBr, •SH, •OOH, and •OOCH3) were investigated along the 273.15–312.15 K temperature range. To that purpose the density functional theory was used, at the M06-2X/6–311+g(d,p) level. Two reaction mechanisms, hydrogen atom transfer (HAT) and radical adduct formation (RAF) were considered. It was found that the relative reactivity of the studied radicals toward limonene is: •SH > •OBr > •OCH3 > •OOH > •OOCH3. HAT was identified as the dominant mechanism for •OOH and •OOCH3, while RAF contributes the most to the reactions involving •OCH3, •OBr, and •SH. The obtained Arrhenius expressions are: k(•OCH3) = 1.58 × 10−13 e−1.59/RT, k(•OBr) = 3.55 × 10−12 e+1.82/RT, k(•SH) = 3.30 × 10−11 e+0.79/RT, k(•OOH) = 1.33 × 10−15 e−5.99/RT, and k(•OOCH3) = 5.88 × 10−17 e−6.26/RT. According to them, the reactions of •OBr and •SH become slower as temperature rises from 273.15 to 312.15 K, while for the other radicals the reactions rate increases with temperature. The subsequent tropospheric fate of the most abundant •OBr adduct was also investigated in the same temperature range, considering O2 addition to this radical (step 2) and the reaction of the peroxyl radical yielded in this step 2 with NO. The latter is predicted to take place in two steps: the NO addition (3a) and the NO2 elimination (3b). The corresponding Arrhenius expression are k2 = 3.56 × 10−15 e+1.43/RT and k3b = 1.35 × 1014 e−31.65/RT. Step 3a was found to be barrierless. To our best knowledge, all the data provided here is reported for the first time. Thus, it would hopefully contribute to enhance the knowledge necessary for the full understanding (and accurate modeling) of the troposphere.
AB - The reactions of limonene with various free radicals (•OCH3, •OBr, •SH, •OOH, and •OOCH3) were investigated along the 273.15–312.15 K temperature range. To that purpose the density functional theory was used, at the M06-2X/6–311+g(d,p) level. Two reaction mechanisms, hydrogen atom transfer (HAT) and radical adduct formation (RAF) were considered. It was found that the relative reactivity of the studied radicals toward limonene is: •SH > •OBr > •OCH3 > •OOH > •OOCH3. HAT was identified as the dominant mechanism for •OOH and •OOCH3, while RAF contributes the most to the reactions involving •OCH3, •OBr, and •SH. The obtained Arrhenius expressions are: k(•OCH3) = 1.58 × 10−13 e−1.59/RT, k(•OBr) = 3.55 × 10−12 e+1.82/RT, k(•SH) = 3.30 × 10−11 e+0.79/RT, k(•OOH) = 1.33 × 10−15 e−5.99/RT, and k(•OOCH3) = 5.88 × 10−17 e−6.26/RT. According to them, the reactions of •OBr and •SH become slower as temperature rises from 273.15 to 312.15 K, while for the other radicals the reactions rate increases with temperature. The subsequent tropospheric fate of the most abundant •OBr adduct was also investigated in the same temperature range, considering O2 addition to this radical (step 2) and the reaction of the peroxyl radical yielded in this step 2 with NO. The latter is predicted to take place in two steps: the NO addition (3a) and the NO2 elimination (3b). The corresponding Arrhenius expression are k2 = 3.56 × 10−15 e+1.43/RT and k3b = 1.35 × 1014 e−31.65/RT. Step 3a was found to be barrierless. To our best knowledge, all the data provided here is reported for the first time. Thus, it would hopefully contribute to enhance the knowledge necessary for the full understanding (and accurate modeling) of the troposphere.
KW - activation energy
KW - atmosphere
KW - kinetics
KW - product distribution
KW - reaction mechanism
KW - temperature dependence
KW - troposphere
UR - http://www.scopus.com/inward/record.url?scp=85148368318&partnerID=8YFLogxK
U2 - 10.1002/qua.27103
DO - 10.1002/qua.27103
M3 - Artículo
AN - SCOPUS:85148368318
SN - 0020-7608
VL - 123
JO - International Journal of Quantum Chemistry
JF - International Journal of Quantum Chemistry
IS - 24
M1 - e27103
ER -