Time-resolved photoelectron imaging of excited state relaxation dynamics in phenol, catechol, resorcinol and hydroquinone

Ruth Livingstone, James Oliver Frank Thompson, Marija Iljina, Ross J Donaldson, Benjamin Sussman, Martin Paterson, David Townsend

Research output: Contribution to journalArticle

Abstract

Time-resolved photoelectron imaging was used to investigate the dynamical evolution of the initially prepared S1 (pp*) excited state of phenol (hydroxybenzene), catechol (1,2-dihydroxybenzene), resorcinol (1,3-dihydroxybenzene), and hydroquinone (1,4-dihydroxybenzene) following excitation at 267 nm. Our analysis was supported by ab initio calculations at the coupled-cluster and CASSCF levels of theory. In all cases, we observe rapid (<1 ps) intramolecular vibrational redistribution on the S1 potential surface. In catechol, the overall S1 state lifetime was observed to be 12.1 ps, which is 1–2 orders of magnitude shorter than in the other three molecules studied. This may be attributed to differences in the H atom tunnelling rate under the barrier formed by a conical intersection between the S1 state and the close lying S2 (ps*) state, which is dissociative along the O–H stretching coordinate. Further evidence of this S1/S2 interaction is also seen in the time-dependent anisotropy of the photoelectron angular distributions we have observed. Our data analysis was assisted by a matrix inversion method for processing photoelectron images that is significantly faster than most other previously reported approaches and is extremely quick and easy to implement.
Original languageEnglish
Article number184304
Number of pages17
JournalJournal of Chemical Physics
Volume137
Issue number18
DOIs
Publication statusPublished - 2012

Fingerprint

Phenol
Anisotropy
resorcinol
hydroquinone
catechol

Cite this

@article{2e393ce69e4f48ae8849dc7e23bea077,
title = "Time-resolved photoelectron imaging of excited state relaxation dynamics in phenol, catechol, resorcinol and hydroquinone",
abstract = "Time-resolved photoelectron imaging was used to investigate the dynamical evolution of the initially prepared S1 (pp*) excited state of phenol (hydroxybenzene), catechol (1,2-dihydroxybenzene), resorcinol (1,3-dihydroxybenzene), and hydroquinone (1,4-dihydroxybenzene) following excitation at 267 nm. Our analysis was supported by ab initio calculations at the coupled-cluster and CASSCF levels of theory. In all cases, we observe rapid (<1 ps) intramolecular vibrational redistribution on the S1 potential surface. In catechol, the overall S1 state lifetime was observed to be 12.1 ps, which is 1–2 orders of magnitude shorter than in the other three molecules studied. This may be attributed to differences in the H atom tunnelling rate under the barrier formed by a conical intersection between the S1 state and the close lying S2 (ps*) state, which is dissociative along the O–H stretching coordinate. Further evidence of this S1/S2 interaction is also seen in the time-dependent anisotropy of the photoelectron angular distributions we have observed. Our data analysis was assisted by a matrix inversion method for processing photoelectron images that is significantly faster than most other previously reported approaches and is extremely quick and easy to implement.",
author = "Ruth Livingstone and Thompson, {James Oliver Frank} and Marija Iljina and Donaldson, {Ross J} and Benjamin Sussman and Martin Paterson and David Townsend",
year = "2012",
doi = "10.1063/1.4765104",
language = "English",
volume = "137",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics Publising LLC",
number = "18",

}

Time-resolved photoelectron imaging of excited state relaxation dynamics in phenol, catechol, resorcinol and hydroquinone. / Livingstone, Ruth; Thompson, James Oliver Frank; Iljina, Marija; Donaldson, Ross J; Sussman, Benjamin; Paterson, Martin; Townsend, David.

In: Journal of Chemical Physics, Vol. 137, No. 18, 184304, 2012.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Time-resolved photoelectron imaging of excited state relaxation dynamics in phenol, catechol, resorcinol and hydroquinone

AU - Livingstone, Ruth

AU - Thompson, James Oliver Frank

AU - Iljina, Marija

AU - Donaldson, Ross J

AU - Sussman, Benjamin

AU - Paterson, Martin

AU - Townsend, David

PY - 2012

Y1 - 2012

N2 - Time-resolved photoelectron imaging was used to investigate the dynamical evolution of the initially prepared S1 (pp*) excited state of phenol (hydroxybenzene), catechol (1,2-dihydroxybenzene), resorcinol (1,3-dihydroxybenzene), and hydroquinone (1,4-dihydroxybenzene) following excitation at 267 nm. Our analysis was supported by ab initio calculations at the coupled-cluster and CASSCF levels of theory. In all cases, we observe rapid (<1 ps) intramolecular vibrational redistribution on the S1 potential surface. In catechol, the overall S1 state lifetime was observed to be 12.1 ps, which is 1–2 orders of magnitude shorter than in the other three molecules studied. This may be attributed to differences in the H atom tunnelling rate under the barrier formed by a conical intersection between the S1 state and the close lying S2 (ps*) state, which is dissociative along the O–H stretching coordinate. Further evidence of this S1/S2 interaction is also seen in the time-dependent anisotropy of the photoelectron angular distributions we have observed. Our data analysis was assisted by a matrix inversion method for processing photoelectron images that is significantly faster than most other previously reported approaches and is extremely quick and easy to implement.

AB - Time-resolved photoelectron imaging was used to investigate the dynamical evolution of the initially prepared S1 (pp*) excited state of phenol (hydroxybenzene), catechol (1,2-dihydroxybenzene), resorcinol (1,3-dihydroxybenzene), and hydroquinone (1,4-dihydroxybenzene) following excitation at 267 nm. Our analysis was supported by ab initio calculations at the coupled-cluster and CASSCF levels of theory. In all cases, we observe rapid (<1 ps) intramolecular vibrational redistribution on the S1 potential surface. In catechol, the overall S1 state lifetime was observed to be 12.1 ps, which is 1–2 orders of magnitude shorter than in the other three molecules studied. This may be attributed to differences in the H atom tunnelling rate under the barrier formed by a conical intersection between the S1 state and the close lying S2 (ps*) state, which is dissociative along the O–H stretching coordinate. Further evidence of this S1/S2 interaction is also seen in the time-dependent anisotropy of the photoelectron angular distributions we have observed. Our data analysis was assisted by a matrix inversion method for processing photoelectron images that is significantly faster than most other previously reported approaches and is extremely quick and easy to implement.

U2 - 10.1063/1.4765104

DO - 10.1063/1.4765104

M3 - Article

VL - 137

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 18

M1 - 184304

ER -