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Photofragment Translational Spectroscopy Studies of H Atom Loss Following Ultraviolet Photoexcitation of Methimazole in the Gas Phase

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Photofragment Translational Spectroscopy Studies of H Atom Loss Following Ultraviolet Photoexcitation of Methimazole in the Gas Phase. / Cooper, Graham A; Hansen, Christopher S; Karsili, Tolga N V; Ashfold, Michael N R .

In: Journal of Physical Chemistry A, Vol. 122, No. 51, 27.12.2018, p. 9869-9878.

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Cooper, Graham A ; Hansen, Christopher S ; Karsili, Tolga N V ; Ashfold, Michael N R . / Photofragment Translational Spectroscopy Studies of H Atom Loss Following Ultraviolet Photoexcitation of Methimazole in the Gas Phase. In: Journal of Physical Chemistry A. 2018 ; Vol. 122, No. 51. pp. 9869-9878.

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@article{707ae3c879474d2295d478a5699e0df8,
title = "Photofragment Translational Spectroscopy Studies of H Atom Loss Following Ultraviolet Photoexcitation of Methimazole in the Gas Phase",
abstract = "The ultraviolet (UV) photodissociation of gas-phase methimazole has been investigated by H Rydberg atom photofragment translational spectroscopy methods at many wavelengths in the range of 222.5–275 nm and by complementary electronic structure calculations. Methimazole is shown to exist predominantly as the thione tautomer, 1-methyl-2(3H)-imidazolinethione, rather than the commonly given thiol form, 2-mercapto-1-methylimidazole. The UV absorption spectrum of methimazole is dominated by the S4 ← S0 transition of the thione tautomer, which involves electron promotion from an a′ (py) orbital localized on the sulfur atom to a σ* orbital localized around the N–H bond. Two H atom formation pathways are identified following UV photoexcitation. One, involving prompt, excited-state N–H bond fission, yields vibrationally cold but rotationally excited methimazolyl (Myl) radicals in their first excited ({\~A}) electronic state. The second yields H atoms with an isotropic recoil velocity distribution peaking at low kinetic energies but extending to the energetic limit allowed by energy conservation given a ground-state dissociation energy D0(Myl–H) ∼24 000 cm–1. These latter H atoms are attributed to the unimolecular decay of highly vibrationally excited S0 parent molecules. The companion electronic structure calculations provide rationales for both fragmentation pathways and the accompanying product energy disposals and highlight similarities and differences between the UV photochemistry of methimazole and that of other azoles (e.g., imidazole) and with molecules like thiourea and thiouracil that contain similar N–C═S motifs.",
author = "Cooper, {Graham A} and Hansen, {Christopher S} and Karsili, {Tolga N V} and Ashfold, {Michael N R}",
year = "2018",
month = "12",
day = "27",
doi = "10.1021/acs.jpca.8b09859",
language = "English",
volume = "122",
pages = "9869--9878",
journal = "Journal of Physical Chemistry A",
issn = "1089-5639",
publisher = "American Chemical Society",
number = "51",

}

RIS - suitable for import to EndNote

TY - JOUR

T1 - Photofragment Translational Spectroscopy Studies of H Atom Loss Following Ultraviolet Photoexcitation of Methimazole in the Gas Phase

AU - Cooper, Graham A

AU - Hansen, Christopher S

AU - Karsili, Tolga N V

AU - Ashfold, Michael N R

PY - 2018/12/27

Y1 - 2018/12/27

N2 - The ultraviolet (UV) photodissociation of gas-phase methimazole has been investigated by H Rydberg atom photofragment translational spectroscopy methods at many wavelengths in the range of 222.5–275 nm and by complementary electronic structure calculations. Methimazole is shown to exist predominantly as the thione tautomer, 1-methyl-2(3H)-imidazolinethione, rather than the commonly given thiol form, 2-mercapto-1-methylimidazole. The UV absorption spectrum of methimazole is dominated by the S4 ← S0 transition of the thione tautomer, which involves electron promotion from an a′ (py) orbital localized on the sulfur atom to a σ* orbital localized around the N–H bond. Two H atom formation pathways are identified following UV photoexcitation. One, involving prompt, excited-state N–H bond fission, yields vibrationally cold but rotationally excited methimazolyl (Myl) radicals in their first excited (Ã) electronic state. The second yields H atoms with an isotropic recoil velocity distribution peaking at low kinetic energies but extending to the energetic limit allowed by energy conservation given a ground-state dissociation energy D0(Myl–H) ∼24 000 cm–1. These latter H atoms are attributed to the unimolecular decay of highly vibrationally excited S0 parent molecules. The companion electronic structure calculations provide rationales for both fragmentation pathways and the accompanying product energy disposals and highlight similarities and differences between the UV photochemistry of methimazole and that of other azoles (e.g., imidazole) and with molecules like thiourea and thiouracil that contain similar N–C═S motifs.

AB - The ultraviolet (UV) photodissociation of gas-phase methimazole has been investigated by H Rydberg atom photofragment translational spectroscopy methods at many wavelengths in the range of 222.5–275 nm and by complementary electronic structure calculations. Methimazole is shown to exist predominantly as the thione tautomer, 1-methyl-2(3H)-imidazolinethione, rather than the commonly given thiol form, 2-mercapto-1-methylimidazole. The UV absorption spectrum of methimazole is dominated by the S4 ← S0 transition of the thione tautomer, which involves electron promotion from an a′ (py) orbital localized on the sulfur atom to a σ* orbital localized around the N–H bond. Two H atom formation pathways are identified following UV photoexcitation. One, involving prompt, excited-state N–H bond fission, yields vibrationally cold but rotationally excited methimazolyl (Myl) radicals in their first excited (Ã) electronic state. The second yields H atoms with an isotropic recoil velocity distribution peaking at low kinetic energies but extending to the energetic limit allowed by energy conservation given a ground-state dissociation energy D0(Myl–H) ∼24 000 cm–1. These latter H atoms are attributed to the unimolecular decay of highly vibrationally excited S0 parent molecules. The companion electronic structure calculations provide rationales for both fragmentation pathways and the accompanying product energy disposals and highlight similarities and differences between the UV photochemistry of methimazole and that of other azoles (e.g., imidazole) and with molecules like thiourea and thiouracil that contain similar N–C═S motifs.

U2 - 10.1021/acs.jpca.8b09859

DO - 10.1021/acs.jpca.8b09859

M3 - Article

VL - 122

SP - 9869

EP - 9878

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

SN - 1089-5639

IS - 51

ER -