60th Ohio State University Symposium on Molecular Spectroscopy • June 20–24, 2005
XTDS:XTDS:A Java-Based Interface to Analyze and A Java-Based Interface to Analyze and Simulate Spectra of Various Molecules Simulate Spectra of Various Molecules
Using Tensorial FormalismUsing Tensorial Formalism
XTDS:XTDS:A Java-Based Interface to Analyze and A Java-Based Interface to Analyze and Simulate Spectra of Various Molecules Simulate Spectra of Various Molecules
Using Tensorial FormalismUsing Tensorial Formalism
Christian WENGER and Vincent BOUDONLaboratoire de Physique de l’Université de Bourgogne – CNRS UMR 5027, 9 Av. A. Savary, BP 47870, F-21078 DIJON, FRANCE
E-mail : [email protected]
Web : http://www.u-bourgogne.fr/LPUB/tSM.html
60th Ohio State University Symposium on Molecular Spectroscopy • June 20–24, 2005
OutlookOutlook
I. Tensorial formalism in molecular spectroscopy
II. Calculating spectra with XTDS
III. Analyzing spectra with XTDS
IV. Conclusion and perspectives
60th Ohio State University Symposium on Molecular Spectroscopy • June 20–24, 2005
I. Tensorial formalism in molecular spectroscopy
I. Tensorial formalism in molecular spectroscopy
60th Ohio State University Symposium on Molecular Spectroscopy • June 20–24, 2005
General ideasGeneral ideas• Use of group theory:
• Symmetry adaptation, O(3) G
• Intermediate symmetry group for « quasi-spherical » molecules, O(3) G’ G
• Use of tensorial formalism:
• Systematic development of the rovibrational Hamiltonian with all interactions
• Systematic development of the transition moments
• Vibrational extrapolation: polyads, global analyses
60th Ohio State University Symposium on Molecular Spectroscopy • June 20–24, 2005
Effective tensorial HamiltonianEffective tensorial Hamiltonian
H Pk{ }
= t s{ } s'{ }Ω K ,nΓ( )ΓvΓv'β RΩ K ,nΓ( ) ⊗ εV s{ } s'{ }
ΓvΓv' Γ( )⎡⎣ ⎤⎦all indexes∑ (A1g )
Systematic tensorial development
H Pn =P Pn HP Pn =H GS{ }
Pn + ...+ H Pk{ }Pn + ...+ H Pn{ }
Pn
Effective Hamiltonian and vibrational extrapolation
ΨrJ ,nC( ) ⊗Ψ v
Cv( )⎡⎣
⎤⎦
Γ( )
Coupled rovibrational basis
H =H P0 ≡GS{ }
+ H P1{ }+ ...+ H Pn{ }
+ ...
Polyad structure
P0
P1
P2
P3
Rotation Vibration
60th Ohio State University Symposium on Molecular Spectroscopy • June 20–24, 2005
Polyad scheme: example of CH4Polyad scheme: example of CH4
Normal modes of methane: ω1 ≈ 2ω2 ≈ω3 ≈ 2ω4
n =2v1 + v2 + 2v3 + v4Definition of polyad Pn:
n = ikvkk∑
General case:
A set of ik integers defines the polyad scheme.
60th Ohio State University Symposium on Molecular Spectroscopy • June 20–24, 2005
Transition moments and intensitiesTransition moments and intensities
μΘ(Γ0 ) = 1;m Θ [Γ] μ {i} C (1g ,Γ ) ⊗M ({i},Γ )⎡
⎣⎤⎦
(Γ0 )
Γ∑
{i}∑
m∑
Dipole moment and absorption intensities
Sif =K ifgie−hcEi /kBT Φi μZ Φ f
2
Mi ,M f
∑
~
~ ~~
αΘ1Θ2
(Γ0 ) = L;m Θ1Θ2 [Γ]α {i} C (Lg ,Γ ) ⊗P({i},Γ )⎡⎣
⎤⎦
(Γ0 )
Γ∑
{i}∑
m∑
L=0,2∑
Polarizability and Raman scattering intensities
Iif =Rifgie−hcEi /kBT Φi αΘ ′Θ Φ f
2
Mi ,M f
∑Θ, ′Θ∑
~
~ ~~
60th Ohio State University Symposium on Molecular Spectroscopy • June 20–24, 2005
The TDS packagesThe TDS packages
http://www.u-bourgogne.fr/LPUB/shTDS.html
XY4 (Td)
XY5Z (C4v)
XY3Z (C3v)
XY6 (Oh)
XY2Z2 (C2v)
60th Ohio State University Symposium on Molecular Spectroscopy • June 20–24, 2005
The TDS packagesThe TDS packages• Series of FORTRAN 77 programs implementing the tensorial
formalism for a given type of molecules.
• Programs launched by UNIX shell scripts.
• XTDS provides a common graphical interface for all the TDS packages.
• This interface allows to build such jobs for various types of problems.
60th Ohio State University Symposium on Molecular Spectroscopy • June 20–24, 2005
II. Calculating spectra with XTDSII. Calculating spectra with XTDS
60th Ohio State University Symposium on Molecular Spectroscopy • June 20–24, 2005
The XTDS applicationThe XTDS application
60th Ohio State University Symposium on Molecular Spectroscopy • June 20–24, 2005
Job creationJob creation
60th Ohio State University Symposium on Molecular Spectroscopy • June 20–24, 2005
Example 1: levels for the dyad of 12CH4Example 1: levels for the dyad of 12CH4
60th Ohio State University Symposium on Molecular Spectroscopy • June 20–24, 2005
Example 1: levels for the dyad of 12CH4Example 1: levels for the dyad of 12CH4
60th Ohio State University Symposium on Molecular Spectroscopy • June 20–24, 2005
Example 2: pentad spectrum of 12CH4Example 2: pentad spectrum of 12CH4
Check this for HITRAN 2004 output (160 characters) !
60th Ohio State University Symposium on Molecular Spectroscopy • June 20–24, 2005
Example 2: pentad spectrum of 12CH4Example 2: pentad spectrum of 12CH4
60th Ohio State University Symposium on Molecular Spectroscopy • June 20–24, 2005
Example 2: pentad spectrum of 12CH4Example 2: pentad spectrum of 12CH4
60th Ohio State University Symposium on Molecular Spectroscopy • June 20–24, 2005
Example 2: pentad spectrum of 12CH4Example 2: pentad spectrum of 12CH4
60th Ohio State University Symposium on Molecular Spectroscopy • June 20–24, 2005
III. Analyzing spectra with XTDSIII. Analyzing spectra with XTDS
60th Ohio State University Symposium on Molecular Spectroscopy • June 20–24, 2005
Example 3: The 2+6 band of 32SF6Example 3: The 2+6 band of 32SF6
60th Ohio State University Symposium on Molecular Spectroscopy • June 20–24, 2005
Example 3: The 2+6 band of 32SF6Example 3: The 2+6 band of 32SF6
60th Ohio State University Symposium on Molecular Spectroscopy • June 20–24, 2005
Example 3: The 2+6 band of 32SF6Example 3: The 2+6 band of 32SF6
60th Ohio State University Symposium on Molecular Spectroscopy • June 20–24, 2005
Example 3: The 2+6 band of 32SF6Example 3: The 2+6 band of 32SF6
Parameter constraintsParameter status:0 = fixed to zero1 = fixed to current value…4 = free
Fit output
60th Ohio State University Symposium on Molecular Spectroscopy • June 20–24, 2005
IV. Conclusion and perspectivesIV. Conclusion and perspectives
60th Ohio State University Symposium on Molecular Spectroscopy • June 20–24, 2005
Practical details - System requirementsPractical details - System requirements
Future developmentsFuture developments
• XTDS runs on UNIX systems : Linux, Mac OS X, …
• Requires a FORTRAN 77 compiler : GNU g77, Absoft f77, …
• Requires a java implementation and SDK
• Improved graphical presentation of results
• New packages: C3V molecules, …
• Stark effect, rovibronic spectroscopy, …