The University of Southampton
University of Southampton Institutional Repository

High-resolution pulsed-field-ionization zero-kinetic-energy photoelectron spectroscopic study of the two lowest electronic states of the ozone cation O3+

High-resolution pulsed-field-ionization zero-kinetic-energy photoelectron spectroscopic study of the two lowest electronic states of the ozone cation O3+
High-resolution pulsed-field-ionization zero-kinetic-energy photoelectron spectroscopic study of the two lowest electronic states of the ozone cation O3+
The pulsed-field-ionization zero-kinetic-energy (PFI-ZEKE) photoelectron spectrum of jet-cooled O-3 has been recorded in the range 101 000-104 000 cm(-1). The origins of the X (1)A(1)-->X+ (2)A(1) and X (1)A(1)-->A(+) B-2(2) transitions could be determined from the rotational structure of the bands, the photoionization selection rules, the photoionization efficiency curve, and comparison with ab initio calculations. The first adiabatic ionization energy of O-3 was measured to be 101 020.5(5) cm(-1) [12.524 95(6) eV] and the energy difference between the X+ (2)A(1) (0,0,0) and A(+) B-2(2) (0,0,0) states was determined to be DeltaT(0)=1089.7(4) cm(-1). Whereas the X-->X+ band consists of an intense and regular progression in the bending (nu(2)) mode observed up to v(2)(+)=4, only the origin of the X-->A(+) band was observed. The analysis of the rotational structure in each band led to the derivation of the r(0) structure of O-3(+) in the X+ [C-2v,r(0)=1.25(2) A,alpha(0)=131.5(9)degrees] and A(+)[C-2v,r(0)=1.37(5) A,alpha(0)=111.3(38)degrees] states. The appearance of the spectrum, which is regular up to 102 300 cm(-1), changes abruptly at approximate to102 500 cm(-1), a position above which the spectral density increases markedly and the rotational structure of the bands collapses. On the basis of ab initio calculations, this behavior is attributed to the onset of large-amplitude motions spreading through several local minima all the way to large internuclear distances. The ab initio calculations are consistent with earlier results in predicting a seam of conical intersections between the X+ and A(+) states approximate to2600 cm(-1) above the cationic ground state and demonstrate the existence of potential minima at large internuclear distances that are connected to the main minima of the X+ and A(+) states through low-lying barriers.
high rydberg states, configuration-interaction, vibrational energies, angular-distribution, dynamics, photoionization, surfaces, spectrum, fluorescence, threshold
0021-9606
024311-[11pp]
Willitsch, Stefan
076aaf36-e87c-4054-86d5-8601cc70e620
Innocenti, Fabrizio
2e95973e-c7b9-4166-8bf2-8b06a713fdfa
Dyke, John M.
46393b45-6694-46f3-af20-d7369d26199f
Merkt, Frederic
b6642eb4-c888-44f4-b065-49ea33d1db74
Willitsch, Stefan
076aaf36-e87c-4054-86d5-8601cc70e620
Innocenti, Fabrizio
2e95973e-c7b9-4166-8bf2-8b06a713fdfa
Dyke, John M.
46393b45-6694-46f3-af20-d7369d26199f
Merkt, Frederic
b6642eb4-c888-44f4-b065-49ea33d1db74

Willitsch, Stefan, Innocenti, Fabrizio, Dyke, John M. and Merkt, Frederic (2005) High-resolution pulsed-field-ionization zero-kinetic-energy photoelectron spectroscopic study of the two lowest electronic states of the ozone cation O3+. The Journal of Chemical Physics, 122 (2), 024311-[11pp]. (doi:10.1063/1.1829974).

Record type: Article

Abstract

The pulsed-field-ionization zero-kinetic-energy (PFI-ZEKE) photoelectron spectrum of jet-cooled O-3 has been recorded in the range 101 000-104 000 cm(-1). The origins of the X (1)A(1)-->X+ (2)A(1) and X (1)A(1)-->A(+) B-2(2) transitions could be determined from the rotational structure of the bands, the photoionization selection rules, the photoionization efficiency curve, and comparison with ab initio calculations. The first adiabatic ionization energy of O-3 was measured to be 101 020.5(5) cm(-1) [12.524 95(6) eV] and the energy difference between the X+ (2)A(1) (0,0,0) and A(+) B-2(2) (0,0,0) states was determined to be DeltaT(0)=1089.7(4) cm(-1). Whereas the X-->X+ band consists of an intense and regular progression in the bending (nu(2)) mode observed up to v(2)(+)=4, only the origin of the X-->A(+) band was observed. The analysis of the rotational structure in each band led to the derivation of the r(0) structure of O-3(+) in the X+ [C-2v,r(0)=1.25(2) A,alpha(0)=131.5(9)degrees] and A(+)[C-2v,r(0)=1.37(5) A,alpha(0)=111.3(38)degrees] states. The appearance of the spectrum, which is regular up to 102 300 cm(-1), changes abruptly at approximate to102 500 cm(-1), a position above which the spectral density increases markedly and the rotational structure of the bands collapses. On the basis of ab initio calculations, this behavior is attributed to the onset of large-amplitude motions spreading through several local minima all the way to large internuclear distances. The ab initio calculations are consistent with earlier results in predicting a seam of conical intersections between the X+ and A(+) states approximate to2600 cm(-1) above the cationic ground state and demonstrate the existence of potential minima at large internuclear distances that are connected to the main minima of the X+ and A(+) states through low-lying barriers.

Text
ozone.pdf - Other
Download (997kB)
Text
20937.pdf - Version of Record
Download (234kB)

More information

Published date: January 2005
Keywords: high rydberg states, configuration-interaction, vibrational energies, angular-distribution, dynamics, photoionization, surfaces, spectrum, fluorescence, threshold
Organisations: Chemistry

Identifiers

Local EPrints ID: 147215
URI: http://eprints.soton.ac.uk/id/eprint/147215
ISSN: 0021-9606
PURE UUID: 58f5973b-ff04-4d5a-84b6-0c3d668487a3
ORCID for John M. Dyke: ORCID iD orcid.org/0000-0002-9808-303X

Catalogue record

Date deposited: 20 May 2010 07:38
Last modified: 05 Nov 2019 02:08

Export record

Altmetrics

Download statistics

Downloads from ePrints over the past year. Other digital versions may also be available to download e.g. from the publisher's website.

View more statistics

Atom RSS 1.0 RSS 2.0

Contact ePrints Soton: eprints@soton.ac.uk

ePrints Soton supports OAI 2.0 with a base URL of http://eprints.soton.ac.uk/cgi/oai2

This repository has been built using EPrints software, developed at the University of Southampton, but available to everyone to use.

We use cookies to ensure that we give you the best experience on our website. If you continue without changing your settings, we will assume that you are happy to receive cookies on the University of Southampton website.

×