مطالعه تئوري سينتيك و مكانيسم اكسيداسيون اتمسفري اسنافتيلن آغاز شده با راديكال هيدروكسيل: مسير ربايش هيدروژن

Theoretical study on the kinetics and mechanism of the atmospheric oxidation of acenaphthylene initiated by hydroxyl radical. Hydrogen Abstraction pathway

در اﯾﻦ ﺗﺤﻘﯿﻖ ﺳﯿﻨﺘﯿﮏ و ﺗﺮﻣﻮدﯾﻨﺎﻣﯿﮏ واﮐﻨﺶ اﺗﻤﺴﻔﺮي رﺑﺎﯾﺶ ﻫﯿﺪروژن از 4ﻣﻮﺿﻊ ﻣﺴﺘﻌﺪ ﻣﻮﻟﮑﻮل آﺳﻨﺎﻓﺘﯿﻠﻦ در ﻓﺎز ﮔﺎزي آﻏﺎز ﺷﺪه ﺗﻮﺳﻂ رادﯾﮑﺎل ﻫﯿﺪروﮐﺴﯿﻞ در ﺳﻄﺢ ﻣﺤﺎﺳﺒﺎﺗﯽ MN15L/aug-cc-pVTZﻣﻮرد ﺑﺮرﺳﯽ ﻗﺮار ﮔﺮﻓﺘﻪ اﺳﺖ. واﮐﻨﺸﻬﺎي رﺑﺎﯾﺶ ﻫﯿﺪروژن از ﻫﺮ 4 ﮐﺎﻧﺎل ﺗﺤﺖ ﻣﻄﺎﻟﻌﻪ ﺧﻮدﺑﺨﻮدي وﮔﺮﻣﺎزا اﺳﺖ. ﻣﻘﺎدﯾﺮ ﺛﻮاﺑﺖ ﺳﺮﻋﺖ )ﺑﺎ و ﺑﺪون اﺻﻼح ﺗﻮﺳﻂ اﺛﺮات ﮐﻮاﻧﺘﻮﻣﯽ ﺗﻮﻧﻠﯽ ﺷﺪن وﯾﮕﻨﺮ و اﯾﮑﺎرت(، اﻧﺮژي ﻫﺎي ﻓﻌﺎﻟﺴﺎزي، و ﺗﻮاﺑﻊ ﺗﺮﻣﻮدﯾﻨﺎﻣﯿﮑﯽ ﻓﻌﺎﻟﺴﺎزي ﺗﺎﯾﯿﺪ ﮐﺮدﻧﺪ ﮐﻪ واﮐﻨﺶ اﺗﻤﺴﻔﺮي رﺑﺎﯾﺶ ﻫﯿﺪروژن آﺳﻨﺎﻓﺘﯿﻠﻦ ﺗﺤﺖ ﮐﻨﺘﺮل ﺳﯿﻨﺘﯿﮑﯽ اﺳﺖ. ﻧﺴﺒﺘﻬﺎي ﺷﺎﺧﻪ اي ﺷﺪن ﻧﺸﺎن دادﻧﺪ ﮐﻪ ﻓﻘﻂ ﻣﺤﺼﻮﻻت رﺑﺎﯾﺶ ﻫﯿﺪروژن از ﻣﻮاﺿﻊ 2و 3و 4 ﻗﺎﺑﻞ ﻣﺸﺎﻫﺪه ﺧﻮاﻫﻨﺪ ﺑﻮد

In this research kinetics and mechanism of the atmospheric hydrogen abstraction of acenaphthylene initiated by hydroxyl radical has been investigated theoretically at the MN15L/aug-cc-pVTZ level of theory. The hydrogen abstraction from the four possible positions are exergonic and exothermic processes. The rate constants (with and without correction by quantum tunneling effects of Wigner and Eckart), activation energies, and activation themodynamic parameters indicated that hydrogen abstraction of acenaphthylene by hydroxyl radical from 4 pathways are kinetically controlled. The values of branching ratios exhibited that the products of hydrogen abstraction reactions from positions 2, 3, and 4 can be observed. . .