Ludovic DaumontLudovic Daumont

Groupe Groupe de de Spectroscopie Moléculaire Spectroscopie Moléculaire et et AtmosphériqueAtmosphérique

UMR CNRS 6089 UMR CNRS 6089

UniversitéUniversité de de Reims Reims Champagne Champagne ArdenneArdenne

ReimsReims, France, France

HDO and D2O long path spectroscopy: Ongoing work of the Brussels-Reims

Team.

Workgroup involved in water vaporWorkgroup involved in water vaporabsorption measurementsabsorption measurements

•• L.L. DaumontDaumont, (M, (M--F. F. MérienneMérienne), L.Regalia), L.Regalia--JarlotJarlot,, VlVl.. TyuterevTyuterev, A. , A. JenouvrierJenouvrierGroupeGroupe dede Spectrométrie MoléculaireSpectrométrie Moléculaire etet AtmosphériqueAtmosphériqueUniversitéUniversité dede ReimsReims ChampagneChampagne--ArdenneArdenne.. ReimsReims, France, France

•• S. S. FallyFally, P, P--F. F. CoheurCoheur, C. , C. ClerbauxClerbaux, M. Bach, M. , M. Bach, M. CarleerCarleerUnitéUnité de de SpectroscopieSpectroscopie AtmosphériqueAtmosphériqueService de Service de ChimieChimie QuantiqueQuantique et et PhotophysiquePhotophysiqueUniversité LibreUniversité Libre de de BruxellesBruxelles. Brussels, Belgium. Brussels, Belgium

•• AA--C. C. VandaeleVandaele, C. , C. HermansHermansInstitutInstitut d’Aéronomied’Aéronomie SpatialeSpatiale de de BelgiqueBelgique. . BruxellesBruxelles, , BelgiqueBelgique

•• A. A. CampargueCampargueLaboratoireLaboratoire de de Spectrométrie Spectrométrie PhysiquePhysiqueUniversitéUniversité de de GrenobleGrenoble, Saint, Saint--MartinMartin--d’Hèresd’Hères, France, France

•• S. S. MikhailenkoMikhailenko, O., O. NaumenkoNaumenko, S. , S. TachkunTachkunInstitut Institut of Atmospheric Optics, of Atmospheric Optics, TomskTomsk, Russia, Russia

•• J.TennysonJ.TennysonDepartment of Physics and Astronomy, University College, EngDepartment of Physics and Astronomy, University College, Englandland

1E-22

1E-17

0 5000 10000 15000 20000 250001E-27

1E-22

1E-17

1E-22

1E-17

1E-22

1E-17

Band Centers cm-1

Inte

grat

edab

sorp

tion

cros

s se

ctio

ns

ΣS(2

96K

) cm

/mol

ec

HOD

H217O

H218O

H216O

HITRAN 2004HITRAN 2004

7250 cm-1

10012 cm-1

13780 cm-1

25120 cm-1

Experimental setupExperimental setup

Sources Xe, W, Globar

Cell (50 m base long )

Cooling or heating system

Temperature controlled Cell(5 m base long )

Laboratory made Spectrometer

Bruker FTSIFS 120M

(ULB or IASB)

Experimental setupExperimental setup

•• Absorption path: 600 m Absorption path: 600 m

•• Resolution: down to 0.03 cmResolution: down to 0.03 cm--11 (30 cm MOPD)(30 cm MOPD)

•• Spectral range: 8800 Spectral range: 8800 -- 10200 cm10200 cm--11

•• HH22O + DO + D22OO mixturesmixtures (( PPtot tot ∼∼ 1010 hPahPa ))

••Room temperature: TRoom temperature: T∼∼ 293 K293 K

••WavenumberWavenumber calibration:calibration: II22 ( table of( table of GesternkornGesternkorn ))

experimental conditionsexperimental conditionsfor HDO for HDO –– DD22O spectraO spectra

diode GaPXe Source

diode SiW Source

7ν+δ

8ν

7ν

6ν+δ 5ν+δ

6ν

5ν

4ν

4ν+δ 3ν

3ν+δ

2ν+δ

diode SiXe Source

VisVis--NIR water absorption spectraNIR water absorption spectra

IR Absorption spectraIR Absorption spectra

diode SiW Source

InSbW Source

InSbW Source

2ν+δ 2ν ν+δν

Observed (H2O & HOD)

Inte

nsity

(a. u

.)

Simulated (H2O)

15260 15258 15256 15254 15252 15250 15248 15246 15244 15242 15240

Subtracted (only HOD lines left)

Wavenumber (cm-1)

VisVis--NIR spectral range: NIR spectral range: Subtraction of the HSubtraction of the H22O linesO lines

85009000950010000105001100011500

0.5

1

1.5

2

910091059110911591209125

0.4

0.9

1.4

1.9

2.4

H2O pure

H2O:3.1%HDO:22.7%D2O:74.2 %

H2O:16.5 %HDO:49.8 %D2O:33.7 %

A

B

C

A / C

C / B

NIR spectral range:NIR spectral range:HH22O, HDO O, HDO andand DD22OO

HDO+D2O

H2O

D2O

H2O+HDO

PathPath: 600 m, P: 13 : 600 m, P: 13 hPahPa, , ResolResol.: 0.03 cm.: 0.03 cm--11

Partial pressures: IR Partial pressures: IR regionregion•Total Pressures: Baratron Ptot

1=P1161+P126

1+P2261 Ptot

2=P1162+P126

2+P2262

•Use of BR list for H216O partial pressures (from natural H2O spectra)

Ptot1=P116

1+P1261+P226

1 Ptot2=P116

2+P1262+P226

2

•Isotopologue assignement => Spectra Ratios

•Line surface measurements => with the good molar mass

•Determination of the mean Surface ratios for HDO and D2O

r1=P1261/P126

2 r2=P2261/P226

2

• Calculation of partial pressures and line intensities

0

2E-24

4E-24

6E-24

8E-24

1E-23

1.2E-23

8800 8900 9000 9100 9200 9300 9400 9500 9600

*

*

*

*

**

*

0

2E-24

4E-24

6E-24

8E-24

1E-23

1.2E-230

2E-24

4E-24

6E-24

8E-24

1E-23

1.2E-23

H20

D2O

HDO

IR IR regionregion: :

HH220, D0, D220 0 andand HDO line HDO line intensitiesintensities

IR IR regionregion: HDO line assignement: HDO line assignementBased on the new calculation of Partridge and Schwenke for both positions and intensities

Still under progress in this region (8800-10200 cm-1)

In the present work

HDO 8800-10200 cm-1 region:

4380 observed lines mainly from 2ν+δ, 3ν and 3ν+δ polyads

5200 assignments

An integrated intensity of 2 10-21 cm molec-1 for this region

D2O: 8800- 13200 cm-1 region:

2160 observed lines mainly from 3ν+δ, 4ν, 4ν+δ and 5ν polyads

2596 assignements

An integrated intensity of 8 10-22 cm molec-1 for this region

Example of aExample of a subbandsubband::νν11+2 +2 νν3 3

∆∆KKaa=0 K=0 K””aa=0=0

9700 9800 9900 10000 101000

4

8

Wavenumber cm-1

-0.10

-0.05

0.00

0

1

2

S(obs)S(PS)

νν obsob

s-- νν c

alc

calc

(cm

(cm

-- 11))

S (1

0-24

cm m

olec

-1)

∆∆KKcc==--11 ∆∆KKcc=1=1Average: 0.95

9800 9900 10000 101000

1

2

-0.2

-0.1

0.0

1

2

Example II of aExample II of a subbandsubband::νν11+2 +2 νν3 3

∆∆KKaa=1 K=1 K””aa=0, =0, ∆∆KKcc=1 =1

S(obs)S(PS)

νν obsob

s-- νν c

alc

calc

(cm

(cm

-- 11))

S (1

0-24

cm m

olec

-1)

Average: 0.97

•• Entire spectral range Entire spectral range →→ Better agreement between different spectral Better agreement between different spectral ranges.ranges.

•• A lot of weak lines A lot of weak lines →→ Better atmospheric spectra simulation.Better atmospheric spectra simulation.

•• Convergence of the theory towards the experimental needs.Convergence of the theory towards the experimental needs.

•• The discrete bands can now be taken off to study the underlyingThe discrete bands can now be taken off to study the underlyingcontinuum.continuum.

•• A lot of unresolved blended lines A lot of unresolved blended lines

••Water vapor pressure measurement still difficult.Water vapor pressure measurement still difficult.

•• Longer absorption paths needed to compare to atmospheric horizoLonger absorption paths needed to compare to atmospheric horizontal ntal (10 (10 -- 20 km) measurement at sea level !20 km) measurement at sea level !

Global commentsGlobal comments

Available Available linelistslinelists and intensitiesand intensities

Continuing workContinuing work

•• IUPACIUPAC-- Water vapor database constitution for all the Water vapor database constitution for all the isotopologues isotopologues

(experience and theory)(experience and theory)•• HODHOD-- DD22OO

-- Measures down to 4200 cmMeasures down to 4200 cm--1 1 (spectra being processed)(spectra being processed)•• HH22OO

-- Analysis of the IR spectra (6600 Analysis of the IR spectra (6600 –– 8800 cm8800 cm--11))•• HH22

1818OO-- …..…..

•• web site fromweb site from ULBULB-- http://www.http://www.ulbulb.ac.be/.ac.be/cpmcpm//datafilesdatafiles.html.html

•• HITRAN 2004HITRAN 2004-- http://http://cfacfa--www.www.harvardharvard..eduedu/HITRAN/HITRAN

•• GEISA 2003GEISA 2003-- http://http://araara..lmdlmd..polytechniquepolytechnique..frfr

IR Absorption spectraIR Absorption spectra

diode SiW Source

InSbW Source

InSbW Source

2ν+δ 2ν ν+δν

The EndThe End

HDO and D2O long path spectroscopy: On going work of the Brussels-Reims

Team.