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A LINE LIST FOR HYDROGEN SULPHIDE (H2S)
Ala’a A. A. Azzam
J. Tennyson and S. Yurchencko
Department of Physics and Astronomy, University College London, UK
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• Colourless gas.• very poisonous.• Flammable.• It has very bad odour.
In volcanic gases. natural gas. some well waters. from the bacterial breakdown of organic matter in the absence of oxygen.
S
HH
S
HH
S
HH
C2V
Symmetric bending Symmetric stretching Asymmetric stretching
ν2 ν1 ν3
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Solve for the motion of electrons
Potential Energy Surface
Dipole Moment Surface
Solve for the motion of nuclei
Spectrum
DVR3D2 program suite is used to calculate the bound ro-vibrational energy levels, wave functions, and dipole transitions intensities using Radau coordinates
MOLPRO1 programEmpirical surface
2J. Tennyson et al. DVR3D: a program suite for the calculation of rotation-vibration spectra of triatomic molecules. Comput. Phys. Commun., 163:85–116, 2004.
1H.-J. Werner et al. Molpro, version 2012.1, a package of ab initio programs, 2012. see http://www.molpro.net.
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Standard deviation values for the error in the calculated ro-vibrational energy levels compared to experimental values up to 17 000 cm−1 for J = 0, 1, 2, 5 and 10. Using newly refined PES3
1. POTENTIAL ENERGY SURFACE (PES)
3V G Tyuterev et al. Chem. Phys. Lett., 348:223–234, 2001. doi: 10.1016/S0009-2614(01)01093-4.
J
Standard deviation (cm−1)
Refined PES Tyuterev et al.’s PES
0 0.19 0.24
1 0.06 0.21
2 0.07 0.21
5 0.07 0.23
10 0.19 0.24
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2. DIPOLE MOMENT SURFACE (DMS)• The fundamental bands of H2S are 2 to 3 orders of magnitude weakerthan in similar triatomic such as H2O and H2Se.
• ν1 and ν3 are much weaker than ν1+ν2 , ν2+ν3 , ν1+ν3
• P-branch (ΔJ=-1) regions of the fundamental bands are much weaker than R-branch (ΔJ=1) regions.
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The effect of the core-electrons correlation and relativistic corrections on the dipole moment ab initio calculations.
L. Lodi, et al. A new ab initio ground-state dipole moment surface for the water molecule. J. Chem. Phys., 128:044304, 2008.
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4Thibaud Cours et al. Ab initio dipole moment function of H2S. Chem. Phys. Lett., 331:317–322, 2000.
Transition intensities accuracy using Cours et al.’s DMS4 up to 4 000 cm-1
J ≤ 5
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J ≤ 5
Transition intensities accuracy using new DMS up to 4 000 cm-1
CCSD(T) / aug-cc-pV(6+d)Z5 + corrections
5T. H. Dunning, et al revisited. J. Chem. Phys., 114:9244, 2001.
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6L. R. Brown, et al J. Mol. Spectrosc., 188: 148–174, 1998.
6
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1L S Rothman et al The HITRAN 2004 molecular spectroscopic database. J. Quant. Spectrosc. Radiat. Transf., 96:139–204, 2005.
21
2http://spectra.iao.ru
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Terahertz spectroscopy of hydrogen sulphide
Ala’a A. A. Azzam, Sergei N. Yurchenko, Jonathan TennysonDepartment of Physics and Astronomy, University College London, London, WC1E 6BT, UK
Marie-Aline Martin-Drumel * and Olivier PiraliCNRS, UMR 8214, Institut des Sciences Mol´eculaires d’Orsay, Universit´e Paris Sud XI, Orsay,
F-91405 Orsay, France and Synchrotron SOLEIL, AILES beamline, F-91192 Gif-Sur-Yvette, France
*Present address: Laboratoire de Physico-Chimie de l’Atmosph`ere, EA 4493, Universit´e du Littotal Cˆote d’Opale, F-59140 Dunkerque, France
Journal of Quantitative Spectroscopy and Radiative Transfer
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Absorption spectrum for H2S in natural abundance recorded at
SOLEIL synchrotron using a globar continuum source
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Comparison for our measured H232S transition positions with
different data resources
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THANK YOU
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Oxygen8O
Sulphur16S
Selenium34Se