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Reaction dynamics of CN radicals with tetrahydrofuran in liquid solutions

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Reaction dynamics of CN radicals with tetrahydrofuran in liquid solutions. / Rose, R. A.; Greaves, S. J.; Abou-Chahine, F.; Glowacki, D. R.; Oliver, T. A. A.; Ashfold, M. N. R.; Clark, I. P.; Greetham, G. M.; Towrie, M.; Orr-Ewing, A. J.

In: Physical Chemistry Chemical Physics, Vol. 14, No. 30, 03.2012, p. 10424-10437.

Research output: Contribution to journalArticle

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Rose, RA, Greaves, SJ, Abou-Chahine, F, Glowacki, DR, Oliver, TAA, Ashfold, MNR, Clark, IP, Greetham, GM, Towrie, M & Orr-Ewing, AJ 2012, 'Reaction dynamics of CN radicals with tetrahydrofuran in liquid solutions', Physical Chemistry Chemical Physics, vol. 14, no. 30, pp. 10424-10437. https://doi.org/10.1039/c2cp40158d

APA

Vancouver

Rose RA, Greaves SJ, Abou-Chahine F, Glowacki DR, Oliver TAA, Ashfold MNR et al. Reaction dynamics of CN radicals with tetrahydrofuran in liquid solutions. Physical Chemistry Chemical Physics. 2012 Mar;14(30):10424-10437. https://doi.org/10.1039/c2cp40158d

Author

Rose, R. A. ; Greaves, S. J. ; Abou-Chahine, F. ; Glowacki, D. R. ; Oliver, T. A. A. ; Ashfold, M. N. R. ; Clark, I. P. ; Greetham, G. M. ; Towrie, M. ; Orr-Ewing, A. J. / Reaction dynamics of CN radicals with tetrahydrofuran in liquid solutions. In: Physical Chemistry Chemical Physics. 2012 ; Vol. 14, No. 30. pp. 10424-10437.

Bibtex

@article{1e63824fa1784bfd8fb332ed2dec1263,
title = "Reaction dynamics of CN radicals with tetrahydrofuran in liquid solutions",
abstract = "Transient, broadband infra-red absorption spectroscopy with picosecond time resolution has been used to study the dynamics of reactions of CN radicals with tetrahydrofuran (THF) and d(8)-THF in liquid solutions ranging from neat THF to 0.5 M THF in chlorinated solvents (CDCl3 and CD2Cl2). HCN and DCN products were monitored via their v(1) (C equivalent to N stretching) and v(3) (C-H(D) stretching) vibrational absorption bands. Transient spectral features indicate formation of vibrationally excited HCN and DCN, and the onsets of absorption via the fundamental bands of HCN and DCN show short (5-15 ps) delays consistent with vibrational relaxation within the nascent reaction products. This interpretation is confirmed by non-equilibrium molecular dynamics simulations employing a newly derived analytic potential energy surface for the reaction in explicit THF solvent. The rate coefficient for reactive formation of HCN (as determined from measurements on both the 1(0)(1) and 3(0)(1) fundamental bands) decreases with increasing dilution of the THF in CDCl3 or CD2Cl2, showing pseudo-first order kinetic behaviour for THF concentrations in the range 0.5-4.5 M, and a bimolecular rate coefficient of (1.57 +/- 0.12) x 10(10) M-1 s(-1) is derived. Simultaneous analysis of time-dependent HCN 1(0)(1) and 3(0)(1) band intensities following reaction of CN with THF (3.0 M) in CD2Cl2 suggests that C-H stretching mode excitation is favoured, and this deduction is supported by the computer simulations. The results extend our recent demonstration of nascent vibrational excitation of the products of bimolecular reactions in liquid solution to a different, and more strongly interacting class of organic solvents. They serve to reinforce the finding that dynamics (and thus the topology of the reactive potential energy surface) play an important role in determining the nascent product state distributions in condensed phase reactions.",
author = "Rose, {R. A.} and Greaves, {S. J.} and F. Abou-Chahine and Glowacki, {D. R.} and Oliver, {T. A. A.} and Ashfold, {M. N. R.} and Clark, {I. P.} and Greetham, {G. M.} and M. Towrie and Orr-Ewing, {A. J.}",
year = "2012",
month = "3",
doi = "10.1039/c2cp40158d",
language = "English",
volume = "14",
pages = "10424--10437",
journal = "Physical Chemistry Chemical Physics",
issn = "1463-9076",
publisher = "The Royal Society of Chemistry",
number = "30",

}

RIS - suitable for import to EndNote

TY - JOUR

T1 - Reaction dynamics of CN radicals with tetrahydrofuran in liquid solutions

AU - Rose, R. A.

AU - Greaves, S. J.

AU - Abou-Chahine, F.

AU - Glowacki, D. R.

AU - Oliver, T. A. A.

AU - Ashfold, M. N. R.

AU - Clark, I. P.

AU - Greetham, G. M.

AU - Towrie, M.

AU - Orr-Ewing, A. J.

PY - 2012/3

Y1 - 2012/3

N2 - Transient, broadband infra-red absorption spectroscopy with picosecond time resolution has been used to study the dynamics of reactions of CN radicals with tetrahydrofuran (THF) and d(8)-THF in liquid solutions ranging from neat THF to 0.5 M THF in chlorinated solvents (CDCl3 and CD2Cl2). HCN and DCN products were monitored via their v(1) (C equivalent to N stretching) and v(3) (C-H(D) stretching) vibrational absorption bands. Transient spectral features indicate formation of vibrationally excited HCN and DCN, and the onsets of absorption via the fundamental bands of HCN and DCN show short (5-15 ps) delays consistent with vibrational relaxation within the nascent reaction products. This interpretation is confirmed by non-equilibrium molecular dynamics simulations employing a newly derived analytic potential energy surface for the reaction in explicit THF solvent. The rate coefficient for reactive formation of HCN (as determined from measurements on both the 1(0)(1) and 3(0)(1) fundamental bands) decreases with increasing dilution of the THF in CDCl3 or CD2Cl2, showing pseudo-first order kinetic behaviour for THF concentrations in the range 0.5-4.5 M, and a bimolecular rate coefficient of (1.57 +/- 0.12) x 10(10) M-1 s(-1) is derived. Simultaneous analysis of time-dependent HCN 1(0)(1) and 3(0)(1) band intensities following reaction of CN with THF (3.0 M) in CD2Cl2 suggests that C-H stretching mode excitation is favoured, and this deduction is supported by the computer simulations. The results extend our recent demonstration of nascent vibrational excitation of the products of bimolecular reactions in liquid solution to a different, and more strongly interacting class of organic solvents. They serve to reinforce the finding that dynamics (and thus the topology of the reactive potential energy surface) play an important role in determining the nascent product state distributions in condensed phase reactions.

AB - Transient, broadband infra-red absorption spectroscopy with picosecond time resolution has been used to study the dynamics of reactions of CN radicals with tetrahydrofuran (THF) and d(8)-THF in liquid solutions ranging from neat THF to 0.5 M THF in chlorinated solvents (CDCl3 and CD2Cl2). HCN and DCN products were monitored via their v(1) (C equivalent to N stretching) and v(3) (C-H(D) stretching) vibrational absorption bands. Transient spectral features indicate formation of vibrationally excited HCN and DCN, and the onsets of absorption via the fundamental bands of HCN and DCN show short (5-15 ps) delays consistent with vibrational relaxation within the nascent reaction products. This interpretation is confirmed by non-equilibrium molecular dynamics simulations employing a newly derived analytic potential energy surface for the reaction in explicit THF solvent. The rate coefficient for reactive formation of HCN (as determined from measurements on both the 1(0)(1) and 3(0)(1) fundamental bands) decreases with increasing dilution of the THF in CDCl3 or CD2Cl2, showing pseudo-first order kinetic behaviour for THF concentrations in the range 0.5-4.5 M, and a bimolecular rate coefficient of (1.57 +/- 0.12) x 10(10) M-1 s(-1) is derived. Simultaneous analysis of time-dependent HCN 1(0)(1) and 3(0)(1) band intensities following reaction of CN with THF (3.0 M) in CD2Cl2 suggests that C-H stretching mode excitation is favoured, and this deduction is supported by the computer simulations. The results extend our recent demonstration of nascent vibrational excitation of the products of bimolecular reactions in liquid solution to a different, and more strongly interacting class of organic solvents. They serve to reinforce the finding that dynamics (and thus the topology of the reactive potential energy surface) play an important role in determining the nascent product state distributions in condensed phase reactions.

UR - http://www.scopus.com/inward/record.url?eid=2-s2.0-84863904186&partnerID=8YFLogxK

U2 - 10.1039/c2cp40158d

DO - 10.1039/c2cp40158d

M3 - Article

C2 - 22499255

VL - 14

SP - 10424

EP - 10437

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

SN - 1463-9076

IS - 30

ER -