Symmetry matters: photodissociation dynamics of symmetrically versus asymmetrically substituted phenols

Tolga N. V. Karsili; Andreas M. Wenge; Barbara Marchetti; Michael N. R. Ashfold

doi:10.1039/c3cp53450b

Symmetry matters: photodissociation dynamics of symmetrically versus asymmetrically substituted phenols

Tolga N. V. Karsili, Andreas M. Wenge, Barbara Marchetti, Michael N. R. Ashfold^*

^*Corresponding author for this work

Research output: Contribution to journal › Article (Academic Journal) › peer-review

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Abstract

We report a combined experimental (H (Rydberg) atom photofragment translational spectroscopy) and theoretical (ab initio electronic structure and vibronic coupling calculations) study of the effects of symmetry on the photodissociation dynamics of phenols. Ultraviolet photoexcitation to the bound S-1((1)(pi pi)*) state of many phenols leads to some O-H bond fission by tunneling through the barrier under the conical intersection (CI) between the S-1 and dissociative S-2(1(pi sigma)*) potential energy surfaces in the RO-H stretch coordinate. Careful analysis of the total kinetic energy release spectra of the resulting products shows that the radicals formed following S-1

Original language	English
Pages (from-to)	588-598
Number of pages	11
Journal	Physical Chemistry Chemical Physics
Volume	16
Issue number	2
Early online date	28 Oct 2013
DOIs	https://doi.org/10.1039/c3cp53450b
Publication status	Published - 28 Oct 2014

Keywords

PHOTOFRAGMENT TRANSLATIONAL SPECTROSCOPY
NEAR-UV PHOTOLYSIS
H-ATOM ELIMINATION
CONICAL INTERSECTIONS
ULTRAVIOLET PHOTOLYSIS
S-1 STATE
O-H
PYRROLE
MOLECULES
HYDROGEN

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NEW HORIZONS IN CHEMICAL AND PHOTOCHEMICAL DYNAMICS
Orr-Ewing, A. J. & Ashfold, M. N. R.
1/10/08 → 1/04/14
Project: Research

Cite this

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title = "Symmetry matters: photodissociation dynamics of symmetrically versus asymmetrically substituted phenols",

abstract = "We report a combined experimental (H (Rydberg) atom photofragment translational spectroscopy) and theoretical (ab initio electronic structure and vibronic coupling calculations) study of the effects of symmetry on the photodissociation dynamics of phenols. Ultraviolet photoexcitation to the bound S-1((1)(pi pi)*) state of many phenols leads to some O-H bond fission by tunneling through the barrier under the conical intersection (CI) between the S-1 and dissociative S-2(1(pi sigma)*) potential energy surfaces in the RO-H stretch coordinate. Careful analysis of the total kinetic energy release spectra of the resulting products shows that the radicals formed following S-1 ",

keywords = "PHOTOFRAGMENT TRANSLATIONAL SPECTROSCOPY, NEAR-UV PHOTOLYSIS, H-ATOM ELIMINATION, CONICAL INTERSECTIONS, ULTRAVIOLET PHOTOLYSIS, S-1 STATE, O-H, PYRROLE, MOLECULES, HYDROGEN",

author = "Karsili, {Tolga N. V.} and Wenge, {Andreas M.} and Barbara Marchetti and Ashfold, {Michael N. R.}",

year = "2014",

month = oct,

day = "28",

doi = "10.1039/c3cp53450b",

language = "English",

volume = "16",

pages = "588--598",

journal = "Physical Chemistry Chemical Physics",

issn = "1463-9076",

publisher = "The Royal Society of Chemistry",

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TY - JOUR

T1 - Symmetry matters: photodissociation dynamics of symmetrically versus asymmetrically substituted phenols

AU - Karsili, Tolga N. V.

AU - Wenge, Andreas M.

AU - Marchetti, Barbara

AU - Ashfold, Michael N. R.

PY - 2014/10/28

Y1 - 2014/10/28

N2 - We report a combined experimental (H (Rydberg) atom photofragment translational spectroscopy) and theoretical (ab initio electronic structure and vibronic coupling calculations) study of the effects of symmetry on the photodissociation dynamics of phenols. Ultraviolet photoexcitation to the bound S-1((1)(pi pi)*) state of many phenols leads to some O-H bond fission by tunneling through the barrier under the conical intersection (CI) between the S-1 and dissociative S-2(1(pi sigma)*) potential energy surfaces in the RO-H stretch coordinate. Careful analysis of the total kinetic energy release spectra of the resulting products shows that the radicals formed following S-1

AB - We report a combined experimental (H (Rydberg) atom photofragment translational spectroscopy) and theoretical (ab initio electronic structure and vibronic coupling calculations) study of the effects of symmetry on the photodissociation dynamics of phenols. Ultraviolet photoexcitation to the bound S-1((1)(pi pi)*) state of many phenols leads to some O-H bond fission by tunneling through the barrier under the conical intersection (CI) between the S-1 and dissociative S-2(1(pi sigma)*) potential energy surfaces in the RO-H stretch coordinate. Careful analysis of the total kinetic energy release spectra of the resulting products shows that the radicals formed following S-1

KW - PHOTOFRAGMENT TRANSLATIONAL SPECTROSCOPY

KW - NEAR-UV PHOTOLYSIS

KW - H-ATOM ELIMINATION

KW - CONICAL INTERSECTIONS

KW - ULTRAVIOLET PHOTOLYSIS

KW - S-1 STATE

KW - O-H

KW - PYRROLE

KW - MOLECULES

KW - HYDROGEN

U2 - 10.1039/c3cp53450b

DO - 10.1039/c3cp53450b

M3 - Article (Academic Journal)

C2 - 24201655

VL - 16

SP - 588

EP - 598

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

SN - 1463-9076

IS - 2

ER -

Symmetry matters: photodissociation dynamics of symmetrically versus asymmetrically substituted phenols

Abstract

Keywords

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