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Title: A study of H2O2 with Threshold Photoelectron Spectroscopy (TPES) and electronic structure calculations : redetermination of the first Adiabatic Ionization Energy (AIE)
Authors: Schio, L
Alagia, M
Dias, AA
Falcinelli, S
Zhaunerchyk, V
Lee, EPF
Mok, DKW 
Dyke, JM
Stranges, S
Issue Date: 14-Jul-2016
Source: Journal of physical chemistry A, 14 July 2016, v. 120, no. 27, p. 5220-5229
Abstract: In this work, hydrogen peroxide has been studied with threshold photoelectron (TPE) spectroscopy and photoelectron (PE) spectroscopy. The TPE spectrum has been recorded in the 10.0-21.0 eV ionization energy region, and the PE spectrum has been recorded at 21.22 eV photon energy. Five bands have been observed which have been assigned on the basis of UCCSD(T)-F12/VQZ-F12 and IP-EOM CCSD calculations. Vibrational structure has only been resolved in the TPE spectrum of the first band, associated with the X2Bg H2O2+ ← X1A H2O2 ionization, on its low energy side. This structure is assigned with the help of harmonic Franck-Condon factor calculations that use the UCCSD(T)-F12a/VQZ-F12 computed adiabatic ionization energy (AIE), and UCCSD(T)-F12a/VQZ-F12 computed equilibrium geometric parameters and harmonic vibrational frequencies for the H2O2 X1A state and the H2O2+ X2Bg state. These calculations show that the main vibrational structure on the leading edge of the first TPE band is in the O-O stretching mode (ω3) and the HOOH deformation mode (ω4), and comparison of the simulated spectrum to the experimental spectrum gives the first AIE of H2O2 as (10.685 ± 0.005) eV and ω4 = (850 ± 30) and ω3 = (1340 ± 30) cm-1 in the X2Bg state of H2O2+. Contributions from ionization of vibrationally excited levels in the torsion mode have been identified in the TPE spectrum of the first band and the need for a vibrationally resolved TPE spectrum from vibrationally cooled molecules, as well as higher level Franck-Condon factors than performed in this work, is emphasized.
Publisher: American Chemical Society
Journal: Journal of physical chemistry A 
ISSN: 1089-5639
DOI: 10.1021/acs.jpca.6b01039
Rights: © 2016 American Chemical Society
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Physical Chemistry A, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see
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