Exploring quantum phenomena and vibrational control in σ* mediated photochemistry

Gareth M. Roberts; David J. Hadden; L. Therese Bergendahl; Andreas M. Wenge; Stephanie J. Harris; Tolga N. V. Karsili; Michael N. R. Ashfold; Martin J. Paterson; Vasilios G. Stavros

doi:10.1039/c2sc21865h

Exploring quantum phenomena and vibrational control in σ* mediated photochemistry

Gareth M. Roberts, David J. Hadden, L. Therese Bergendahl, Andreas M. Wenge, Stephanie J. Harris, Tolga N. V. Karsili, Michael N. R. Ashfold^*, Martin J. Paterson, Vasilios G. Stavros

^*Corresponding author for this work

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

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Abstract

Non-adiabatic dynamics involving (1)pi sigma* or (1)n sigma* excited electronic states play a key role in the photochemistry of numerous heteroatom containing aromatic (bio-) molecules. In this contribution, we investigate more exotic phenomena involved in sigma* mediated dynamics, namely: (i) the role of purely quantum mechanical behavior; and (ii) manipulating non-adiabatic photochemistry through conical intersections (CIs) with 'vibration-specific control'. This is achieved by investigating S-CH3 bond fission via a (1)n sigma* potential energy surface (PES) in thioanisole (C6H5SCH3). Using a combination of time- and frequency-resolved velocity map ion imaging techniques, together with ab initio calculations, we demonstrate that excitation to the (1)pi pi* ...

Original language	English
Pages (from-to)	993-1001
Number of pages	9
Journal	Chemical Science
Volume	4
Issue number	3
Early online date	29 Nov 2012
DOIs	https://doi.org/10.1039/c2sc21865h
Publication status	Published - 2013

Keywords

STATES
THIOPHENOL
SPECTROSCOPY
PHOTOELECTRON
UV PHOTODISSOCIATION
DYNAMICS
CONICAL INTERSECTIONS

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Chem Sci 2013 4 993Final published version, 502 KB

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@article{e2f4bbd47c7e4394b3b560cc6bebe505,

title = "Exploring quantum phenomena and vibrational control in σ* mediated photochemistry",

abstract = "Non-adiabatic dynamics involving (1)pi sigma* or (1)n sigma* excited electronic states play a key role in the photochemistry of numerous heteroatom containing aromatic (bio-) molecules. In this contribution, we investigate more exotic phenomena involved in sigma* mediated dynamics, namely: (i) the role of purely quantum mechanical behavior; and (ii) manipulating non-adiabatic photochemistry through conical intersections (CIs) with 'vibration-specific control'. This is achieved by investigating S-CH3 bond fission via a (1)n sigma* potential energy surface (PES) in thioanisole (C6H5SCH3). Using a combination of time- and frequency-resolved velocity map ion imaging techniques, together with ab initio calculations, we demonstrate that excitation to the (1)pi pi* ...",

keywords = "STATES, THIOPHENOL, SPECTROSCOPY, PHOTOELECTRON, UV PHOTODISSOCIATION, DYNAMICS, CONICAL INTERSECTIONS",

author = "Roberts, {Gareth M.} and Hadden, {David J.} and Bergendahl, {L. Therese} and Wenge, {Andreas M.} and Harris, {Stephanie J.} and Karsili, {Tolga N. V.} and Ashfold, {Michael N. R.} and Paterson, {Martin J.} and Stavros, {Vasilios G.}",

year = "2013",

doi = "10.1039/c2sc21865h",

language = "English",

volume = "4",

pages = "993--1001",

journal = "Chemical Science",

issn = "2041-6520",

publisher = "Royal Society of Chemistry",

number = "3",

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T1 - Exploring quantum phenomena and vibrational control in σ* mediated photochemistry

AU - Roberts, Gareth M.

AU - Hadden, David J.

AU - Bergendahl, L. Therese

AU - Wenge, Andreas M.

AU - Harris, Stephanie J.

AU - Karsili, Tolga N. V.

AU - Ashfold, Michael N. R.

AU - Paterson, Martin J.

AU - Stavros, Vasilios G.

PY - 2013

Y1 - 2013

N2 - Non-adiabatic dynamics involving (1)pi sigma* or (1)n sigma* excited electronic states play a key role in the photochemistry of numerous heteroatom containing aromatic (bio-) molecules. In this contribution, we investigate more exotic phenomena involved in sigma* mediated dynamics, namely: (i) the role of purely quantum mechanical behavior; and (ii) manipulating non-adiabatic photochemistry through conical intersections (CIs) with 'vibration-specific control'. This is achieved by investigating S-CH3 bond fission via a (1)n sigma* potential energy surface (PES) in thioanisole (C6H5SCH3). Using a combination of time- and frequency-resolved velocity map ion imaging techniques, together with ab initio calculations, we demonstrate that excitation to the (1)pi pi* ...

AB - Non-adiabatic dynamics involving (1)pi sigma* or (1)n sigma* excited electronic states play a key role in the photochemistry of numerous heteroatom containing aromatic (bio-) molecules. In this contribution, we investigate more exotic phenomena involved in sigma* mediated dynamics, namely: (i) the role of purely quantum mechanical behavior; and (ii) manipulating non-adiabatic photochemistry through conical intersections (CIs) with 'vibration-specific control'. This is achieved by investigating S-CH3 bond fission via a (1)n sigma* potential energy surface (PES) in thioanisole (C6H5SCH3). Using a combination of time- and frequency-resolved velocity map ion imaging techniques, together with ab initio calculations, we demonstrate that excitation to the (1)pi pi* ...

KW - STATES

KW - THIOPHENOL

KW - SPECTROSCOPY

KW - PHOTOELECTRON

KW - UV PHOTODISSOCIATION

KW - DYNAMICS

KW - CONICAL INTERSECTIONS

U2 - 10.1039/c2sc21865h

DO - 10.1039/c2sc21865h

M3 - Article (Academic Journal)

SN - 2041-6520

VL - 4

SP - 993

EP - 1001

JO - Chemical Science

JF - Chemical Science

IS - 3

ER -

Exploring quantum phenomena and vibrational control in σ* mediated photochemistry

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Keywords

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