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A Multipronged Comparative Study of the Ultraviolet Photochemistry of 2-, 3-, and 4-Chlorophenol in the Gas Phase

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A Multipronged Comparative Study of the Ultraviolet Photochemistry of 2-, 3-, and 4-Chlorophenol in the Gas Phase. / Harris, S J; Karsili, T N V; Murdock, D; Oliver, T A A; Wenge, A M; Zaouris, D K; Ashfold, M N R; Harvey, J N; Few, J D; Gowrie, S; Hancock, G; Hadden, D J; Roberts, G M; Stavros, V G; Spighi, G; Poisson, L; Soep, B.

In: Journal of Physical Chemistry A, Vol. 119, No. 23, 11.06.2015, p. 6045-56.

Research output: Contribution to journalArticle

Harvard

Harris, SJ, Karsili, TNV, Murdock, D, Oliver, TAA, Wenge, AM, Zaouris, DK, Ashfold, MNR, Harvey, JN, Few, JD, Gowrie, S, Hancock, G, Hadden, DJ, Roberts, GM, Stavros, VG, Spighi, G, Poisson, L & Soep, B 2015, 'A Multipronged Comparative Study of the Ultraviolet Photochemistry of 2-, 3-, and 4-Chlorophenol in the Gas Phase' Journal of Physical Chemistry A, vol. 119, no. 23, pp. 6045-56. https://doi.org/10.1021/jp511879k

APA

Harris, S. J., Karsili, T. N. V., Murdock, D., Oliver, T. A. A., Wenge, A. M., Zaouris, D. K., ... Soep, B. (2015). A Multipronged Comparative Study of the Ultraviolet Photochemistry of 2-, 3-, and 4-Chlorophenol in the Gas Phase. Journal of Physical Chemistry A, 119(23), 6045-56. https://doi.org/10.1021/jp511879k

Vancouver

Harris SJ, Karsili TNV, Murdock D, Oliver TAA, Wenge AM, Zaouris DK et al. A Multipronged Comparative Study of the Ultraviolet Photochemistry of 2-, 3-, and 4-Chlorophenol in the Gas Phase. Journal of Physical Chemistry A. 2015 Jun 11;119(23):6045-56. https://doi.org/10.1021/jp511879k

Author

Harris, S J ; Karsili, T N V ; Murdock, D ; Oliver, T A A ; Wenge, A M ; Zaouris, D K ; Ashfold, M N R ; Harvey, J N ; Few, J D ; Gowrie, S ; Hancock, G ; Hadden, D J ; Roberts, G M ; Stavros, V G ; Spighi, G ; Poisson, L ; Soep, B. / A Multipronged Comparative Study of the Ultraviolet Photochemistry of 2-, 3-, and 4-Chlorophenol in the Gas Phase. In: Journal of Physical Chemistry A. 2015 ; Vol. 119, No. 23. pp. 6045-56.

Bibtex

@article{0e4f6821c39d431a93fcb1d31ebc0d6f,
title = "A Multipronged Comparative Study of the Ultraviolet Photochemistry of 2-, 3-, and 4-Chlorophenol in the Gas Phase",
abstract = "The S1((1)ππ*) state of the (dominant) syn-conformer of 2-chlorophenol (2-ClPhOH) in the gas phase has a subpicosecond lifetime, whereas the corresponding S1 states of 3- and 4-ClPhOH have lifetimes that are, respectively, ∼2 and ∼3-orders of magnitude longer. A range of experimental techniques-electronic spectroscopy, ultrafast time-resolved photoion and photoelectron spectroscopies, H Rydberg atom photofragment translational spectroscopy, velocity map imaging, and time-resolved Fourier transform infrared emission spectroscopy-as well as electronic structure calculations (of key regions of the multidimensional ground (S0) state potential energy surface (PES) and selected cuts through the first few excited singlet PESs) have been used in the quest to explain these striking differences in excited state lifetime. The intramolecular O-H···Cl hydrogen bond specific to syn-2-ClPhOH is key. It encourages partial charge transfer and preferential stabilization of the diabatic (1)πσ* potential (relative to that of the (1)ππ* state) upon stretching the C-Cl bond, with the result that initial C-Cl bond extension on the adiabatic S1 PES offers an essentially barrierless internal conversion pathway via regions of conical intersection with the S0 PES. Intramolecular hydrogen bonding is thus seen to facilitate the type of heterolytic dissociation more typically encountered in solution studies.",
author = "Harris, {S J} and Karsili, {T N V} and D Murdock and Oliver, {T A A} and Wenge, {A M} and Zaouris, {D K} and Ashfold, {M N R} and Harvey, {J N} and Few, {J D} and S Gowrie and G Hancock and Hadden, {D J} and Roberts, {G M} and Stavros, {V G} and G Spighi and L Poisson and B Soep",
year = "2015",
month = "6",
day = "11",
doi = "10.1021/jp511879k",
language = "English",
volume = "119",
pages = "6045--56",
journal = "Journal of Physical Chemistry A",
issn = "1089-5639",
publisher = "American Chemical Society",
number = "23",

}

RIS - suitable for import to EndNote

TY - JOUR

T1 - A Multipronged Comparative Study of the Ultraviolet Photochemistry of 2-, 3-, and 4-Chlorophenol in the Gas Phase

AU - Harris, S J

AU - Karsili, T N V

AU - Murdock, D

AU - Oliver, T A A

AU - Wenge, A M

AU - Zaouris, D K

AU - Ashfold, M N R

AU - Harvey, J N

AU - Few, J D

AU - Gowrie, S

AU - Hancock, G

AU - Hadden, D J

AU - Roberts, G M

AU - Stavros, V G

AU - Spighi, G

AU - Poisson, L

AU - Soep, B

PY - 2015/6/11

Y1 - 2015/6/11

N2 - The S1((1)ππ*) state of the (dominant) syn-conformer of 2-chlorophenol (2-ClPhOH) in the gas phase has a subpicosecond lifetime, whereas the corresponding S1 states of 3- and 4-ClPhOH have lifetimes that are, respectively, ∼2 and ∼3-orders of magnitude longer. A range of experimental techniques-electronic spectroscopy, ultrafast time-resolved photoion and photoelectron spectroscopies, H Rydberg atom photofragment translational spectroscopy, velocity map imaging, and time-resolved Fourier transform infrared emission spectroscopy-as well as electronic structure calculations (of key regions of the multidimensional ground (S0) state potential energy surface (PES) and selected cuts through the first few excited singlet PESs) have been used in the quest to explain these striking differences in excited state lifetime. The intramolecular O-H···Cl hydrogen bond specific to syn-2-ClPhOH is key. It encourages partial charge transfer and preferential stabilization of the diabatic (1)πσ* potential (relative to that of the (1)ππ* state) upon stretching the C-Cl bond, with the result that initial C-Cl bond extension on the adiabatic S1 PES offers an essentially barrierless internal conversion pathway via regions of conical intersection with the S0 PES. Intramolecular hydrogen bonding is thus seen to facilitate the type of heterolytic dissociation more typically encountered in solution studies.

AB - The S1((1)ππ*) state of the (dominant) syn-conformer of 2-chlorophenol (2-ClPhOH) in the gas phase has a subpicosecond lifetime, whereas the corresponding S1 states of 3- and 4-ClPhOH have lifetimes that are, respectively, ∼2 and ∼3-orders of magnitude longer. A range of experimental techniques-electronic spectroscopy, ultrafast time-resolved photoion and photoelectron spectroscopies, H Rydberg atom photofragment translational spectroscopy, velocity map imaging, and time-resolved Fourier transform infrared emission spectroscopy-as well as electronic structure calculations (of key regions of the multidimensional ground (S0) state potential energy surface (PES) and selected cuts through the first few excited singlet PESs) have been used in the quest to explain these striking differences in excited state lifetime. The intramolecular O-H···Cl hydrogen bond specific to syn-2-ClPhOH is key. It encourages partial charge transfer and preferential stabilization of the diabatic (1)πσ* potential (relative to that of the (1)ππ* state) upon stretching the C-Cl bond, with the result that initial C-Cl bond extension on the adiabatic S1 PES offers an essentially barrierless internal conversion pathway via regions of conical intersection with the S0 PES. Intramolecular hydrogen bonding is thus seen to facilitate the type of heterolytic dissociation more typically encountered in solution studies.

U2 - 10.1021/jp511879k

DO - 10.1021/jp511879k

M3 - Article

VL - 119

SP - 6045

EP - 6056

JO - Journal of Physical Chemistry A

T2 - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

SN - 1089-5639

IS - 23

ER -