Transcript WF13.pptx

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.
C2V
 In volcanic gases.
 natural gas.
 some well waters.
 from the bacterial breakdown of
organic matter in the absence of oxygen.
S
H
H
Symmetric bending
ν2
S
S
H
H
Symmetric stretching
ν1
H
H
Asymmetric stretching
ν3
Solve for the motion of
electrons
Potential Energy Surface
Dipole Moment Surface
Empirical surface
MOLPRO1 program
Solve for the motion of nuclei
DVR3D2 program suite is used to calculate the bound ro-vibrational energy levels,
wave functions, and dipole transitions intensities using Radau coordinates
Spectrum
1H.-J.
2J.
Werner et al. Molpro, version 2012.1, a package of ab initio programs, 2012. see http://www.molpro.net.
Tennyson et al. DVR3D: a program suite for the calculation of rotation-vibration spectra of triatomic
molecules. Comput. Phys. Commun., 163:85–116, 2004.
1. POTENTIAL ENERGY SURFACE (PES)
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
Standard deviation (cm−1)
3V
J
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
G Tyuterev et al. Chem. Phys. Lett., 348:223–234, 2001. doi: 10.1016/S0009-2614(01)01093-4.
2. DIPOLE MOMENT SURFACE (DMS)
• The fundamental bands of H2S are 2 to 3 orders of magnitude weaker
than 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 Rbranch (ΔJ=1) regions.
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.
Transition intensities accuracy using Cours et al.’s DMS4 up to 4 000 cm-1
J≤5
4Thibaud
Cours et al. Ab initio dipole moment function of H2S. Chem. Phys. Lett., 331:317–322, 2000.
Transition intensities accuracy using new DMS up to 4 000 cm-1
CCSD(T) / aug-cc-pV(6+d)Z5 + corrections
J≤5
5T.
H. Dunning, et al revisited. J. Chem. Phys., 114:9244, 2001.
6
6L.
R. Brown, et al J. Mol. Spectrosc., 188: 148–174, 1998.
1
1L
2
S Rothman et al The HITRAN 2004 molecular spectroscopic database. J. Quant. Spectrosc. Radiat.
Transf., 96:139–204, 2005.
2http://spectra.iao.ru
Terahertz spectroscopy of hydrogen sulphide
Ala’a A. A. Azzam, Sergei N. Yurchenko, Jonathan Tennyson
Department of Physics and Astronomy, University College London, London, WC1E 6BT, UK
Marie-Aline Martin-Drumel * and Olivier Pirali
CNRS, 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
Absorption spectrum for H2S in natural abundance recorded at
SOLEIL synchrotron using a globar continuum source
Comparison for our measured H232S transition positions with
different data resources
THANK YOU
Oxygen
8
O
Sulphur
16
S
Selenium
34
Se