Présentation PowerPoint - Harvard-Smithsonian Center for ...

Présentation PowerPoint - Harvard-Smithsonian Center for ...

Recent knowledge of spectroscopic parameters for Acetylene in the IR
D. Jacquemart,a N. Lacome, a V. Dana,b J.-Y. Mandin b, O.M. Lyulin c,
c
d
d
d
V.I. Perevalov , L. Rgalia-Jarlot , X. Thomas , P. Von Der Heyden
Laboratoire de Dynamique, Interactions et Ractivit, Universit Pierre-et-Marie Curie, CNRS, UMR 7075, Case courrier 49,
4, place Jussieu, 75252 Paris Cedex 05, France
b
Laboratoire de Physique Molculaire pour lAtmosphre et lAstrophysique, Universit Pierre-et-Marie-Curie, CNRS, UMR 7092,
Case courrier 76,4, place Jussieu,75252 Paris Cedex 05, France
c
Institute of Atmospheric Optics, Siberian Branch, Russian Academy of Sciences, 1, Akademicheskii av.,634055 Tomsk, Russia
d
Groupe de Spectromtrie Molculaire et Atmosphrique, Universit de Reims-Champagne-Ardenne, CNRS, BP 1039, 51687 Reims Cedex, France.
a

13.6

PRESENTATION
The acetylene molecule is important for atmospheric,
planetary, and astrophysics applications. In order to improve

and 2.2-m spectral region. (submitted to m spectral regions. = (HITRAN2004 - this

0

10

20

2.3x10

-4

-30

-20

-10

0

-4

2,0x10

-4

1,8x10

-4

1,6x10

2+(4+5)0+ - 41

-4

1,4x10

-30

-20

-10

0

10

6,5x10

6,0x10

-4

-4

5,5x10

-4

5,0x10

-4

4,5x10

-4

4,0x10

20

obs for the P- and R-branches
calc for the P- and R-branches
obs for the Q-branch
calc for the Q-branch

1 - 51

-4

-30

-20

-10

0

m

10

20

-6

1,8x10

0

(34+5) +

-6

1,6x10

1+(4+25)1 51

-6

2x10

-6

1x10

m

0

-6

1,2x10

-25

30

-20

-15

-10

-5

0

5

10

15

20

m

-10

0

10

20

2x10

-6

2+(44+5)1 41
-6

m

30

-20

-15

-10

-5

0

5

10

15

2
-6

1,5x10

1+(4+5)0+
-6

1,0x10

m

-7

5,0x10

20

-30

-20

-10

0

10

20

-6

1,0x10

-7

5,0x10

2+(34+5)0+

m
0,0
-30

30

Transition dipole moment squared in debye

2

6x10

-6

5x10

-6

4x10

-6

3x10

1+(24+5) 5
1

-6

2x10

1

-6

1x10

0
-30

m
-20

-10

0

10

20

-6

2,5x10

-6

2,0x10

-6

1,5x10

3+341 41

-6

1,0x10

-7

5,0x10

m

0,0
-20

-10

0

10

20

-20

-10

0

10

20

30

2

Transition dipole moment squared in debye

Transition dipole moment squared in debye

2

Transition dipole moment squared in debye

-6

-7

4x10

-7

3x10

3+250

-7

2x10

-7

1x10

m

0
-30

-20

-10

Transition dipole moment squared in debye

2

10

20

30

0

-5

6x10

-5

4x10

-5

2x10

m
-40

40

-30

-20

-10

0

10

20

30

40

2

Transition dipole moment squared in debye

1+51

1,0x10

-5

5,0x10

m
-30

-20

-10

0

10

20

30

-6

1x10

2+351

-7

9x10

-7

8x10

-7

7x10

-7

6x10

-7

5x10

-7

4x10

m

-7

3x10

-20

40

-4

2,5x10

1+250 51

-4

2,0x10

-4

1,5x10

-4

1,0x10

-5

5,0x10

m
-20

-10

0

10

20

-10

0

10

20

30

-4

4x10

1+252 51
-4

3x10

-4

2x10

-4

1x10

m
-30

30

10

20

30

-4

1x10

-5

9x10

1+(4+5)0+ 41

-5

8x10

-5

7x10

-5

6x10

-5

5x10

-5

4x10

-5

3x10

-5

2x10

m

-5

1x10

-40

2

-20

3x10

0

-4

Transition dipole moment squared in debye

-6

3x10

-10

3+41

-20

-10

0

10

20

30

-30

-20

-10

0

10

20

-4

1x10

1+(4+5)0 41

-5

9x10

-5

8x10

-5

7x10

-5

6x10

-5

5x10

-5

4x10

-5

3x10

m
-40

30

-30

-20

-10

0

10

20

30

2

4x10

-20

-6

Transition dipole moment squared in debye

-6

4x10

Transition dipole moment squared in debye 2

2

Transition dipole moment squared in debye

2

Transition dipole moment squared in debye

-6

5x10

-6

-30

1,4x10

Results at 2.2 microns
6x10

m

-30

m

-6

-5

2x10

-5

8x10

2

2

2

Squared dipole transition moment (in Debye )

2,2x10

30

m

obs for the P- and R-branches
calc for the P- and R-branches
obs for the Q-branch
calc for the Q-branch

-4

20

-5

4x10

-4

Transition dipole moment squared in debye

2,4x10

10

-5

6x10

-40

2.2x10

m
-4

obs
Spectrum 1 calculated
Spectrum 2 calculated
Spectrum 3 calculated
Spectrum 4 calculated

0

-4

30

2

2

obs for the P- and R-branches
calc for the P- and R-branches
obs for the Q-branch
calc for the Q-branch

2+(24+5)1 II

2

-4

-5

1,5x10

2

-10

2.7x10

2

Squared dipole transition moment (in Debye )

-20

F (m) 1 A m(m 1)

6x10

-7

5x10

-7

4x10

-7

3x10

-7

2x10

-7

1x10

-7

1+(4+5)2 41

0,015

-5

5x10

m
-30

3+24

Global treatment of P = 4 and 6 series

-4

1x10

-20

-10

0

10

20

0

30

0,010

0,005

0,000

-0,005

-0,010
2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

m

0
-30

-20

-10

0

Wavenumber in cm
10

20

-1

30

CONCLUSION
Several collaborations between LADIR, LPMAA, GSMA, and LTS has led to the better knowledge of the acetylene IR spectroscopic parameters in the 2.2, 2.5, and 3.8-m spectral region. (submitted to m
spectral regions. The experimental results in the 2.5 and 3.8-m spectral region. (submitted to m regions have allowed the generation of line lists with calculated positions (obtained from polynomial fits of
measurements), and calculated intensities (using the transition dipole moment and the Herman-Wallis coefficients of each band). This has not been done for the 2.2-m spectral region. (submitted to m region
where strong interactions between levels do not allow accurate fit using Herman-Wallis coefficients. All the measurements have then been used to treat the P = 4, 6 and 7 P = 4, 6 and 7
series. The first results are encouraging, but at that time the precision of the line positions and intensities obtained using treatment of the Hamiltonian and the transition dipole
moment, is not enough accurate compared to the one from experimental measurements. The global model of acetylene done by LTS (Perevalov et al.) still need some
improvement, and measurements to achieve the experimental accuracy that is better than 10-3 cm-1 for positions, and 5% for line intensities. Note that, the predictability of
this model was successfully tested on two hot bands of the 2.5-m spectral region. (submitted to m region [2].

Observed - Predicted intensities in %

-5

1.6x10

-4

-4

Q
2

-1

-5

1.8x10

-4

2.8x10

2.4x10

(m) (1 A m A m )

Q

Observed - Predicted positions in cm

2.0x10

-4

2.9x10

2.5x10

2 2

Transition dipole moment squared in debye

-5

-4

3.0x10

-4

RP
2

Transition dipole moment squared in debye

3-4

2.6x10

RP
1

2

Transition dipole moment squared in debye

1

Transition dipole moment squared in debye

-5

2.2x10

RP

8x10

-40

1,4 cm-1

Transmission

-5

2.4x10

gl

2

C2H2 in 4 spectra recorded at

12

different pressures. The calculated spectra reproduce very
well each experimental spectrum. For each of them, the
residuals (obs-calc) of the fit are quite good despite the two
channels (due to windows) present in the experimental
spectra. The residuals of the fit do not exceed 2%.

Transition dipole moment squared in debye

-5

2.6x10

0

Results at 2.5 microns

2

Squared dipole transition moment (in Debye )

2

Squared dipole transition moment (in Debye )

work

F

Transition dipole moment squared in debye

branch of the 2 + 51 of

1

obs for the P- and R-branches
calc for the P- and R-branches
obs for the Q-branch
calc for the Q-branch

-5

1

B 0

3hc Z tot (T0 )

)/

spectrum. Combining the absolute accuracy from
HITRAN2004 and the statistic deviation of our wavenumber
calibration, we estimated that the absolute accuracy of the
measured positions is around 0.0005 cm-1.
As an example of the capability of our multispectrum fitting
procedure, this figure shows a simultaneous fit of the Q-

Results at 3.8 microns
2.8x10

HITRAN2004 has been calculated for isolated transitions in each

-1

3.1x10

1.7

moment) are fitting for each P-and R-branch and Q-branch the following equations:

H2O transitions and C2H2 transitions respectively for the 2.5-

v1 = 3373 cm ; v2 = 1974 cm ; v3 = 3294 cm ;
v4 = 613 cm-1 ; v5 = 730 cm-1

3.0x10

1.9

band of 12C16O2 has been used for the 3.8-m spectral region. (submitted to m spectral region; The quantities F(m) (calculated using the Herman Wallis coefficients), and |R0| (vibrational dipole transition

P = 5v1 + 3v2 + 5v3 + v4 + v5 .

-4

0

separately for the three spectral regions. Transitions of the 3

the studied spectral region concerns the series of vibrational
transitions P = 4, 6 and 7 with P the pseudo-quantum number:

2+51

2.2

m

B 0

through cold and hot bands). According to Perevalovs notation,

-5

2.5

0

C2H2 (interacting

-1

3

-1

vibrational states belonging to different polyads are taken into account

-1

3.8

700
1300
2100
2600
3300
4000
4600
5200
5900

9600
To retrieve absolute line positions and intensities from the
cm
spectra, a multispectrum fitting procedure [6] has been
used. Because of the wide variety of the line strength values,
Polyads defined by P the pseudo-quantum number: P = 5v1 + 3v2 + 5v3 + v4 + v5
1
2
3
4
5
6
7
8
9

15
the best experimental conditions for an accurate analysis are
P
obtained only for two or three spectra. Due to the flexibility
of the multispectrum procedure, we were able to adjust
ANALYSIS OF THE SQUARED DIPOLE TRANSITION MOMENT
simultaneously all experimental spectra. Let us recall that the
position, intensity, and broadening coefficient of a same line The determination of the squared dipole transition moment R2 is obtained from the line intensity using the
following equation:
in the five spectra keep the same values during the fit.
hcE
hc
3

2
2
0
gs
2
k
T
In a first step, a wavenumber calibration has been done
N
36 8
k T

R R F ( m)
k (T ) 10
e
1 e
R L( J , )

measurements of line parameters have been performed. Three
recent works in three different spectral regions are presented: in
the 3.8-m regionm region, where 2 cold and 3 hot bands have been
studied [1]; in the 2.5-m regionm region, where 4 cold and 5 hot bands
have been studied [2]; in the 2.2-m regionm region, where 4 cold and 4
hot bands have been studied [3]. Line positions and intensities
have been analysed. In these three spectral regions, transition
dipole moments squared values have been derived from the line
intensity measurements, and have been modelled using HermanWallis factors.
No analysis of absolute individual line intensities in these three
regions has been done before these present works. Line lists
have been generated and will be proposed to atmospheric and
planetary spectroscopic databases. The analysis of these spectral
region has also allowed to improve the global theoretical
treatment [4-5] of Perevalov et al. adapted to the Hamiltonian
12

5

MEASUREMENT PROCEDURE

the knowledge of C2H2 spectroscopic parameters, systematic

and transition dipole moment of acetylene

7.7

10

5

0

-5

-10

2400 2600 2800 3000 3200 3400 3600 3800 4000 4200 4400

Wavenumber in cm

-1

References:
[1] D. Jacquemart, N. Lacome, J.-Y. Mandin, V. Dana, O.M. Lyulin, V.I. Perevalov. Multispectrum fitting of line parameters for 12C2H2 in the 3.8-m spectral region. (submitted to m spectral region. (submitted to JQSRT)
[2] O.M. Lyulin, V.I. Perevalov, J.-Y. Mandin, V. Dana, F. Gueye, X. Thomas, P. Von Der Heyden, D. Dcatoire, L. Rgalia-Jarlot, D. Jacquemart, N. Lacome. Line intensities of acetylene: Measurements in the 2.5-m spectral region and global modeling in the P = 4 and 6 series. (submitted to JQSRT)
[3] O.M. Lyulin A, V.I. Perevalov, F. Gueye, J.-Y. Mandin, V. Dana, X. Thomas, P. Von Der Heyden, L. Rgalia-Jarlot, A. Barbe. Line intensities of acetylene. Measurements in the 2.2-m spectral region and global modeling in the P = 7 series (under editing)
[4] O.M. Lyulin, V.I. Perevalov, S.A. Tashkun, and J.-L. Teffo. Global fitting of the vibrational-rotational line positions of acetylene molecule in the far and middle infrared regions. In: Proceedings of the XIVth Symposium on High-Resolution Molecular Spectroscopy, Krosnoyarsk, Russia. SPIE 5311, 134-143 (2004).
[5] V.I. Perevalov, O.M. Lyulin, D. Jacquemart, C. Claveau, J.-L. Teffo, V. Dana, J.-Y. Mandin, and A. Valentin. Global fitting of line intensities of acetylene molecule in the infrared using the effective operator approach. J Mol Spectrosc 218, 180-189 (2003).
[6] D. Jacquemart, J.-Y. Mandin, V. Dana, N. Picqu, and G. Guelachvili. A multispectrum fitting procedure to deduce molecular line parameters. Application to the 30 band of 12C16O. Eur Phys J D 14, 55-69 (2001).

Recently Viewed Presentations

  • Satan Is Busy - Simple Bible Studies

    Satan Is Busy - Simple Bible Studies

    Satan Is Busy. So we need to resist him even more. How Busy Is Satan? "Be sober, be vigilant; because your adversary the devil, as a roaring lion, walketh about, seeking whom he may devour." (1 Pet. 5:8) Satan Is...
  • PDCB BioC for HTS topic Understanding the tech. 02

    PDCB BioC for HTS topic Understanding the tech. 02

    PDCB BioC for HTS topicUnderstanding the tech. 02. LCG Leonardo Collado Torres. [email protected] [email protected] September 2nd, 2010
  • State Board - New Jersey

    State Board - New Jersey

    Marie B Office of the Secretary of Higher Education Received Lumina Foundation Grant New Jersey received a $100,000 attainment challenge grant from the Lumina Foundation to help increase the state's postsecondary adult attainment rate to 65 percent by 2025.
  • ENEMY FORCES  SAPA are well trained and very

    ENEMY FORCES SAPA are well trained and very

    COMMANDS. Stop Alto . Do not move No se mueva. Pass Pase. Turn around Dé la vuelta alrededor. Lower your hands Baje las manos. Drop your weapons Suelte sus armas
  • Comparison between self & separately controlled synchronous ...

    Comparison between self & separately controlled synchronous ...

    Motor must have wound field rotor. By varying field current motor power factor can be varied. Power factor calculator receives voltage and current feedback signals and calculates pf of motor. CONSTANT MARGINAL ANGLE CONTROL. PERMANENT MAGNET SYNCHRONOUS MOTOR DRIVES.
  • Empire Electric Health Outcomes Report Active Population ...

    Empire Electric Health Outcomes Report Active Population ...

    Data Mining Mining what already happened The view from executive leadership and what was learned: Communication strategy was key Big difference between predictive modeling that has high accuracy rates and other rules/stratifiers/ retrospective looks at claims in terms of finding...
  • Managing Difficult Conversations - WSHA Home Page

    Managing Difficult Conversations - WSHA Home Page

    Use beliefs if the signals tell you it's appropriate. It's O.K. to acknowledge share beliefs, but DON'T impose yours. "He's in a better place" can be reassuring or assaultive. It's O.K. to touch a hand or shoulder, but let others...
  • CYP Programme

    CYP Programme

    CYP Programme. A Pan Dorset Emotional Well-being and Mental Health Strategy for Children and Young People is in place for 2016-20 and this is led by a local partnership between NHS Dorset CCG, Dorset County Council, Borough of Poole, Bournemouth...