60th Ohio State University Symposium on Molecular Spectroscopy June 20–24, 2005 XTDS: A Java-Based...

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


OutlookOutlook

I. Tensorial formalism in molecular spectroscopy

II. Calculating spectra with XTDS

III. Analyzing spectra with XTDS

IV. Conclusion and perspectives


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


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


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.


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∑

~

~ ~~


The TDS packagesThe TDS packages

http://www.u-bourgogne.fr/LPUB/shTDS.html

XY4 (Td)

XY5Z (C4v)

XY3Z (C3v)

XY6 (Oh)

XY2Z2 (C2v)


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.


II. Calculating spectra with XTDSII. Calculating spectra with XTDS


The XTDS applicationThe XTDS application


Job creationJob creation


Example 1: levels for the dyad of 12CH4Example 1: levels for the dyad of 12CH4


Example 2: pentad spectrum of 12CH4Example 2: pentad spectrum of 12CH4

Check this for HITRAN 2004 output (160 characters) !


Example 2: pentad spectrum of 12CH4Example 2: pentad spectrum of 12CH4


III. Analyzing spectra with XTDSIII. Analyzing spectra with XTDS


Example 3: The 2+6 band of 32SF6Example 3: The 2+6 band of 32SF6


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


IV. Conclusion and perspectivesIV. Conclusion and perspectives


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, …

60th Ohio State University Symposium on Molecular Spectroscopy June 20–24, 2005 XTDS: A Java-Based...

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