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Comparing molecular photofragmentation dynamics in the gas and liquid phases

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Comparing molecular photofragmentation dynamics in the gas and liquid phases. / Harris, Stephanie J.; Murdock, Daniel; Zhang, Yuyuan; Oliver, Thomas A.A.; Grubb, Michael P.; Orr-Ewing, Andrew J.; Greetham, Gregory M.; Clark, Ian P.; Towrie, Michael; Bradforth, Stephen E.; Ashfold, Michael N. R.

In: Physical Chemistry Chemical Physics, Vol. 15, No. 18, 14.05.2013, p. 6567-6582.

Research output: Contribution to journalArticle

Harvard

Harris, SJ, Murdock, D, Zhang, Y, Oliver, TAA, Grubb, MP, Orr-Ewing, AJ, Greetham, GM, Clark, IP, Towrie, M, Bradforth, SE & Ashfold, MNR 2013, 'Comparing molecular photofragmentation dynamics in the gas and liquid phases', Physical Chemistry Chemical Physics, vol. 15, no. 18, pp. 6567-6582. https://doi.org/10.1039/c3cp50756d

APA

Harris, S. J., Murdock, D., Zhang, Y., Oliver, T. A. A., Grubb, M. P., Orr-Ewing, A. J., ... Ashfold, M. N. R. (2013). Comparing molecular photofragmentation dynamics in the gas and liquid phases. Physical Chemistry Chemical Physics, 15(18), 6567-6582. https://doi.org/10.1039/c3cp50756d

Vancouver

Harris SJ, Murdock D, Zhang Y, Oliver TAA, Grubb MP, Orr-Ewing AJ et al. Comparing molecular photofragmentation dynamics in the gas and liquid phases. Physical Chemistry Chemical Physics. 2013 May 14;15(18):6567-6582. https://doi.org/10.1039/c3cp50756d

Author

Harris, Stephanie J. ; Murdock, Daniel ; Zhang, Yuyuan ; Oliver, Thomas A.A. ; Grubb, Michael P. ; Orr-Ewing, Andrew J. ; Greetham, Gregory M. ; Clark, Ian P. ; Towrie, Michael ; Bradforth, Stephen E. ; Ashfold, Michael N. R. / Comparing molecular photofragmentation dynamics in the gas and liquid phases. In: Physical Chemistry Chemical Physics. 2013 ; Vol. 15, No. 18. pp. 6567-6582.

Bibtex

@article{a27142234f4748d2b382c7629b599bbe,
title = "Comparing molecular photofragmentation dynamics in the gas and liquid phases",
abstract = "This article explores the extent to which insights gleaned from detailed studies of molecular photodissociations in the gas phase (i.e. under isolated molecule conditions) can inform our understanding of the corresponding photofragmentation processes in solution. Systems selected for comparison include a thiophenol (p-methylthiophenol), a thioanisole (p-methylthioanisole) and phenol, in vacuum and in cyclohexane solution. UV excitation in the gas phase results in RX-Y (X = O, S; Y = H, CH3) bond fission in all cases, but over timescales that vary by similar to 4 orders of magnitude - all of which behaviours can be rationalised on the basis of the relevant bound and dissociative excited state potential energy surfaces (PESs) accessed by UV photoexcitation, and of the conical intersections that facilitate radiationless transfer between these PESs. Time-resolved UV pump-broadband UV/visible probe and/or UV pump-broadband IR probe studies of the corresponding systems in cyclohexane solution reveal additional processes that are unique to the condensed phase. Thus, for example, the data clearly reveal evidence of (i) vibrational relaxation of the photoexcited molecules prior to their dissociation and of the radical fragments formed upon X-Y bond fission, and (ii) geminate recombination of the RX and Y products (leading to reformation of the ground state parent and/or isomeric adducts). Nonetheless, the data also show that, in each case, the characteristics (and the timescale) of the initial bond fission process that occurs under isolated molecule conditions are barely changed by the presence of a weakly interacting solvent like cyclohexane. These condensed phase studies are then extended to an ether analogue of phenol (allyl phenyl ether), wherein UV photo-induced RO-allyl bond fission constitutes the first step of a photo-Claisen rearrangement.",
keywords = "GEMINATE RECOMBINATION, RESOLVED INFRARED-ABSORPTION, CHEMICAL-REACTIVITY, TRANSIENT ELECTRONIC ABSORPTION, FRAGMENT ROTATIONAL-DYNAMICS, PHOTODISSOCIATION DYNAMICS, EXCITED SINGLET-STATE, VIBRATIONAL-RELAXATION, REAL-TIME, RESONANCE RAMAN-SPECTROSCOPY",
author = "Harris, {Stephanie J.} and Daniel Murdock and Yuyuan Zhang and Oliver, {Thomas A.A.} and Grubb, {Michael P.} and Orr-Ewing, {Andrew J.} and Greetham, {Gregory M.} and Clark, {Ian P.} and Michael Towrie and Bradforth, {Stephen E.} and Ashfold, {Michael N. R.}",
year = "2013",
month = "5",
day = "14",
doi = "10.1039/c3cp50756d",
language = "English",
volume = "15",
pages = "6567--6582",
journal = "Physical Chemistry Chemical Physics",
issn = "1463-9076",
publisher = "The Royal Society of Chemistry",
number = "18",

}

RIS - suitable for import to EndNote

TY - JOUR

T1 - Comparing molecular photofragmentation dynamics in the gas and liquid phases

AU - Harris, Stephanie J.

AU - Murdock, Daniel

AU - Zhang, Yuyuan

AU - Oliver, Thomas A.A.

AU - Grubb, Michael P.

AU - Orr-Ewing, Andrew J.

AU - Greetham, Gregory M.

AU - Clark, Ian P.

AU - Towrie, Michael

AU - Bradforth, Stephen E.

AU - Ashfold, Michael N. R.

PY - 2013/5/14

Y1 - 2013/5/14

N2 - This article explores the extent to which insights gleaned from detailed studies of molecular photodissociations in the gas phase (i.e. under isolated molecule conditions) can inform our understanding of the corresponding photofragmentation processes in solution. Systems selected for comparison include a thiophenol (p-methylthiophenol), a thioanisole (p-methylthioanisole) and phenol, in vacuum and in cyclohexane solution. UV excitation in the gas phase results in RX-Y (X = O, S; Y = H, CH3) bond fission in all cases, but over timescales that vary by similar to 4 orders of magnitude - all of which behaviours can be rationalised on the basis of the relevant bound and dissociative excited state potential energy surfaces (PESs) accessed by UV photoexcitation, and of the conical intersections that facilitate radiationless transfer between these PESs. Time-resolved UV pump-broadband UV/visible probe and/or UV pump-broadband IR probe studies of the corresponding systems in cyclohexane solution reveal additional processes that are unique to the condensed phase. Thus, for example, the data clearly reveal evidence of (i) vibrational relaxation of the photoexcited molecules prior to their dissociation and of the radical fragments formed upon X-Y bond fission, and (ii) geminate recombination of the RX and Y products (leading to reformation of the ground state parent and/or isomeric adducts). Nonetheless, the data also show that, in each case, the characteristics (and the timescale) of the initial bond fission process that occurs under isolated molecule conditions are barely changed by the presence of a weakly interacting solvent like cyclohexane. These condensed phase studies are then extended to an ether analogue of phenol (allyl phenyl ether), wherein UV photo-induced RO-allyl bond fission constitutes the first step of a photo-Claisen rearrangement.

AB - This article explores the extent to which insights gleaned from detailed studies of molecular photodissociations in the gas phase (i.e. under isolated molecule conditions) can inform our understanding of the corresponding photofragmentation processes in solution. Systems selected for comparison include a thiophenol (p-methylthiophenol), a thioanisole (p-methylthioanisole) and phenol, in vacuum and in cyclohexane solution. UV excitation in the gas phase results in RX-Y (X = O, S; Y = H, CH3) bond fission in all cases, but over timescales that vary by similar to 4 orders of magnitude - all of which behaviours can be rationalised on the basis of the relevant bound and dissociative excited state potential energy surfaces (PESs) accessed by UV photoexcitation, and of the conical intersections that facilitate radiationless transfer between these PESs. Time-resolved UV pump-broadband UV/visible probe and/or UV pump-broadband IR probe studies of the corresponding systems in cyclohexane solution reveal additional processes that are unique to the condensed phase. Thus, for example, the data clearly reveal evidence of (i) vibrational relaxation of the photoexcited molecules prior to their dissociation and of the radical fragments formed upon X-Y bond fission, and (ii) geminate recombination of the RX and Y products (leading to reformation of the ground state parent and/or isomeric adducts). Nonetheless, the data also show that, in each case, the characteristics (and the timescale) of the initial bond fission process that occurs under isolated molecule conditions are barely changed by the presence of a weakly interacting solvent like cyclohexane. These condensed phase studies are then extended to an ether analogue of phenol (allyl phenyl ether), wherein UV photo-induced RO-allyl bond fission constitutes the first step of a photo-Claisen rearrangement.

KW - GEMINATE RECOMBINATION

KW - RESOLVED INFRARED-ABSORPTION

KW - CHEMICAL-REACTIVITY

KW - TRANSIENT ELECTRONIC ABSORPTION

KW - FRAGMENT ROTATIONAL-DYNAMICS

KW - PHOTODISSOCIATION DYNAMICS

KW - EXCITED SINGLET-STATE

KW - VIBRATIONAL-RELAXATION

KW - REAL-TIME

KW - RESONANCE RAMAN-SPECTROSCOPY

U2 - 10.1039/c3cp50756d

DO - 10.1039/c3cp50756d

M3 - Article

VL - 15

SP - 6567

EP - 6582

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

SN - 1463-9076

IS - 18

ER -