pressure-broadening of water lines in the thz frequency region: improvements and confirmations for...
TRANSCRIPT
Pressure-broadening of water lines Pressure-broadening of water lines in the THz frequency region: in the THz frequency region:
improvements and confirmations improvements and confirmations for spectroscopic databasesfor spectroscopic databases
G. Cazzoli, G. Cazzoli, C. PuzzariniC. PuzzariniDipartimento di Chimica “G. Ciamician”, Università Dipartimento di Chimica “G. Ciamician”, Università
di Bolognadi Bologna
G. BuffaG. BuffaIPCF-CNR and Dipartimento di Fisica "E. Fermi", PisaIPCF-CNR and Dipartimento di Fisica "E. Fermi", Pisa
10th International HITRAN Conference 10th International HITRAN Conference — 22-24 June, 2008— 22-24 June, 2008
OUTLINESOUTLINES
1) Experimental set-up:1) Experimental set-up: The THz spectrometerThe THz spectrometer
2) Theoretical calculations:2) Theoretical calculations: The semiclassical approachThe semiclassical approach
1) Experimental details:1) Experimental details: The THz spectrometer The THz spectrometer
2) Theoretical calculations:2) Theoretical calculations: The semiclassical approachThe semiclassical approach
3) Experiment & Theory:3) Experiment & Theory: ResultsResults3) Experiment & Theory:3) Experiment & Theory: ResultsResults
1) Experimental details:1) Experimental details: The THz spectrometerThe THz spectrometer - set up- set up - techniques- techniques - procedure - procedure
1) Experimental details:1) Experimental details: The THz spectrometerThe THz spectrometer - - set upset up - techniques- techniques - procedure - procedure
FREQUENCY RANGE covered @ LMSBFREQUENCY RANGE covered @ LMSB
(2) 50-600 GHz (from fundamental to the 6th harmonic) (2) 50-600 GHz (from fundamental to the 6th harmonic) + 600-800 GHz (8th harmonic)+ 600-800 GHz (8th harmonic)
(3)(3) 1.0-1.2 THz (9th harmonic) 1.0-1.2 THz (9th harmonic) + 1.33-1.6 THz (12th harmonic)+ 1.33-1.6 THz (12th harmonic)
(1) 8-120 GHz (wave-guide Stark cell – P band) (1) 8-120 GHz (wave-guide Stark cell – P band)
(3) 1.0-1.2 THz (9th harmonic) (3) 1.0-1.2 THz (9th harmonic) + 1.33-1.6 THz (12th harmonic)+ 1.33-1.6 THz (12th harmonic)
BLOCK DIAGRAM of the 1.0-1-6 THz SPECTROMETER
MULTIPLIER
SYNTH10 kHz-1 GHzMULT fS
nfS
MIXMULT
SYNCRref: 20 MHz
RF OSCILL3.7- 7.6 GHz
fRF
20 MHz
73 MHz|fG - mfRF |
GUNN P. SUPPLY and
SYNCRref: 73 MHz
|fRF - nfS|
HP8642ASYNTH
MIX
corr
fG
GeDETECTOR
PREAMPL
10 MHzfreq. standard
ref
GUNNDIODES CELL
FUNCTIONGENERATOR
300 Hz
CHOPPERCHOPPER
LOCK-INAMPLIFIER
FREQUENCY MODULATION TECHNIQUEFREQUENCY MODULATION TECHNIQUE
2x frequency modualtion2x frequency modualtion
BLOCK DIAGRAM of the 1.0-1-6 THz SPECTROMETER
MULTIPLIER
SYNTH10 kHz-1 GHzMULT fS
nfS
MIXMULT
SYNCRref: 20 MHz
RF OSCILL3.7- 7.6 GHz
fRF
20 MHz
73 MHz|fG - mfRF |
GUNN P. SUPPLY and
SYNCRref: 73 MHz
|fRF - nfS|
HP8642ASYNTH
MIX
corr
fG
GeDETECTOR
PREAMPL
10 MHzfreq. standard
ref
GUNNDIODES CELL
FUNCTIONGENERATOR
300 Hz
CHOPPERCHOPPER
LOCK-INAMPLIFIER
AMPLITUDE MODULATION TECHNIQUEAMPLITUDE MODULATION TECHNIQUE
chopper frequency revolutionchopper frequency revolution
(3) EXPERIMENTAL SET-UP (3) EXPERIMENTAL SET-UP in thein the THz REGION THz REGION
Quartz cell (1cm long) THz scource (gunn + multiplier)
ChopperBolometer
The 1.0-1.6 THz The 1.0-1.6 THz SPECTROMETERSPECTROMETER
(3) EXPERIMENTAL SET-UP (3) EXPERIMENTAL SET-UP in thein the THz REGION THz REGIONThe 1.0-1.2 THz The 1.0-1.2 THz SPECTROMETERSPECTROMETER
THz scourceTHz scource
Cell Cell
1) Experimental details:1) Experimental details: The THz spectrometerThe THz spectrometer - set up- set up - techniques- techniques - procedure - procedure
1) Experimental details:1) Experimental details: The THz spectrometerThe THz spectrometer - set up- set up - - techniquestechniques - procedure - procedure
AMPLITUDE MODULATION TECHNIQUEAMPLITUDE MODULATION TECHNIQUE
1146550 1146600 1146650
Frequency (MHz)
Self-broadening: J = 72,5 - 8
1,8
residuals x 3
Natural line Natural line profileprofile
Lambert-Beer Lambert-Beer lawlaw
II = = II00 exp[ exp[((--00))LL]]
LINE SHAPE ANALYSISLINE SHAPE ANALYSISTo retrieve To retrieve COLLISIONAL HALF-WIDTH COLLISIONAL HALF-WIDTH LL:: by fitting the observed line profiles – natural line profiles - by fitting the observed line profiles – natural line profiles - directlydirectly to the chosen line profile model (Voigt profile, to the chosen line profile model (Voigt profile, Galatry profile, Speed Dependent Voigt profile, … …)Galatry profile, Speed Dependent Voigt profile, … …)
1146550 1146600 1146650
Frequency (MHz)
Self-broadening: J = 72,5 - 8
1,8
residuals x 3
Residuals:Residuals:Obs. – Calc.Obs. – Calc.
SOURCE MODULATION TECHNIQUESOURCE MODULATION TECHNIQUEFREQUENCY MODULATIONFREQUENCY MODULATION (sine wave): (sine wave):
((tt)) = = (( - - 00)) + + cos cos mmtt
== modulation modulation depthdepth mm== modulation modulation frequencyfrequency
K(x, y, z) K(x, y, z) = Voigt, Galatry or SP-Voigt or … function= Voigt, Galatry or SP-Voigt or … function
Line profile expanded in a cosine Fourier Line profile expanded in a cosine Fourier series.series.
2nd harmonic detection:2nd harmonic detection: aa2 2 (() = 2/) = 2/ K(x,y,z) cos 2K(x,y,z) cos 2
dd
00301805 301810 301815 301820 301825
O3: 301.8 GHZ line
O2-broadening
T = 296 K
40.4139.5240.1342.5447.2
FREQUENCY (MHz)
Validity:Validity: Absorption Absorption 6% 6%
II = = II00 [1- [1- ((--00))LL]]
LINE SHAPE ANALYSISLINE SHAPE ANALYSISCOLLISIONAL HALF-WIDTH COLLISIONAL HALF-WIDTH LL:: by fitting the observed line profiles to a by fitting the observed line profiles to a model that model that explicitly accounts for frequency modulationexplicitly accounts for frequency modulation [Cazzoli & Dore JMS 141, 49 (1990); Dore JMS 221, 93 (2003)].
301805 301810 301815 301820 301825
O3: 301.8 GHZ line
O2-broadening
T = 296 K
40.4139.5240.1342.5447.2
FREQUENCY (MHz)
Residuals:Residuals:Obs. – Calc.Obs. – Calc.
1) Experimental details:1) Experimental details: The THz spectrometerThe THz spectrometer - set up- set up - techniques- techniques - procedure - procedure
1) Experimental details:1) Experimental details: The THz spectrometerThe THz spectrometer - set up- set up - techniques- techniques - - procedureprocedure
LINE SHAPE ANALYSIS:LINE SHAPE ANALYSIS:Which line Which line profile model?profile model?
301805 301810 301815 301820 301825
Frequency (MHz)
Voigt profileVoigt profile301805 301810 301815 301820 301825
Frequency (MHz)
Galatry profileGalatry profile
The 301.8 GHz line of OThe 301.8 GHz line of O33 broadened by N broadened by N22
LINE SHAPE ANALYSIS:LINE SHAPE ANALYSIS:Which line Which line profile model?profile model?
301810 301811 301812 301813 301814 301815 301816
301.8 GHz line of O3:
O2-broadening at T=240 K
PO2
= 201.8 mTorr
Frequency (MHz)
EXP VP obs-calc (VP) obs-calc (SDVP) obs-calc (GP)
(a)
(b)
(c)
(d)
LINE SHAPE ANALYSIS:LINE SHAPE ANALYSIS:Which line Which line profile model?profile model?LINE SHAPE ANALYSIS:LINE SHAPE ANALYSIS:Which line Which line profile model?profile model?Galatry vs Speed-dependent Voigt profileGalatry vs Speed-dependent Voigt profile
0 200 400 600 800 1000
0
500
1000
1500
2000
2500
3000
3500
4000
rela
xatio
n rate
(kH
z)
PO2
(mTorr)
317.2 GHz line of O3:
O2-broadening at T=240 K
SDV rate in blue (SDVP)
2 rate in blue (SDVP)
rate in red (GP)
RETRIEVAL PARAMETERSRETRIEVAL PARAMETERS
0 50 100 150 200 250 300 350 400 4500
200
400
600
800
1000
1200
1400
1600
L (kH
z)
Pperturb (mTorr)
PRESSURE BROADENING COEFFICIENT PRESSURE BROADENING COEFFICIENT
:: by a weighted linear fit of linear fit of LL against against PP
perturbperturb
00
L L == 0 0 + + perturbperturb P Pperturbperturb
Lorentzian halfwidthLorentzian halfwidth
Broadening due to absorberBroadening due to absorber
0 100 200 300 400 5006.552
6.554
6.556
6.558
6.560
6.562
6.564
6.566
6.568
Fre
quency (M
Hz)
Pperturb
(mTorr)
RETRIEVAL PARAMETERSRETRIEVAL PARAMETERS
PRESSURE SHIFT COEFFICIENT sPRESSURE SHIFT COEFFICIENT s:: by a weighted linear fit of linear fit of against against PP
== 0 0 + s+ sperturbperturb P Pperturb perturb
Transition frequencyTransition frequency
Frequency at PFrequency at Ppertubpertub = 0 = 0ss
00
2) Theoretical calculations:2) Theoretical calculations: The semiclassical approach The semiclassical approach 2) Theoretical calculations:2) Theoretical calculations: The semiclassical approachThe semiclassical approach
THEORETICAL DETAILSTHEORETICAL DETAILS
COLLISIONAL RELAXATIONCOLLISIONAL RELAXATION described within the IMPACT APPROXIMATION by the EFFICIENCY FUNCTION EFFICIENCY FUNCTION PP.
For a line i f PP = 1 - < i | S | i ><f | St | f >
S = scattering matrix, H0 = Hamiltonian of internal degrees, V = collisional interaction, O = time ordering operator.
SEMICLASSICAL APPROXIMATIONSEMICLASSICAL APPROXIMATION (impact parameter bb, relative velocity v, internal state of perturber r): PP = = PP((b,v,rb,v,r)).
The linewidth linewidth and lineshift lineshift ss: real and imaginary parts of PP:
r = population of level r, f(v) = Maxwellian velocity distribution, n = perturber density.
dtetVeOS tiHtiH
// )(exp 00
1
r
rdb r v b bP dv v vf n is00
2) , , ( ) (
3) Experiment & Theory:3) Experiment & Theory: ResultsResults - H- H22O: which linesO: which lines - theo & exp results:- theo & exp results: detailed comparisondetailed comparison
3) Experiment & Theory:3) Experiment & Theory: ResultsResults - - HH22O: which linesO: which lines - theo & exp results:- theo & exp results: detailed comparisondetailed comparison
JJ = 3 = 31,21,2 - 3 - 30,30,3** (1.097 THz) (1.097 THz) JJ = 1 = 11,11,1 - 0 - 00,00,0
(1.113 THz) (1.113 THz) JJ = 7 = 72,52,5 - 8 - 81,81,8
(1.147 THz) (1.147 THz) JJ = 3 = 31,21,2 - 2 - 22,12,1** (1.153 THz) (1.153 THz) JJ = 6 = 63,43,4 - 5 - 54,14,1** (1.158 THz) (1.158 THz) JJ = 3 = 32,12,1 - 3 - 31,21,2** (1.163 THz) (1.163 THz) JJ = 8 = 85,45,4 - 7 - 76,16,1
(1.168 THz) (1.168 THz) JJ = 7 = 74,44,4 - 6 - 65,15,1
(1.173 THz) (1.173 THz) JJ = 8 = 85,35,3 - 7 - 76,26,2
(1.191 THz) (1.191 THz) JJ = 6 = 63,33,3 - 5 - 54,24,2
(1.542 THz) (1.542 THz)
HH22O: THz pure rotational lines investigatedO: THz pure rotational lines investigated
Self-broad:Self-broad:amplitude modulationamplitude modulation
NN22- - && O O22-broad -broad frequency modulationfrequency modulation
Self-broad:Self-broad:amplitude modulationamplitude modulation
NN22- - && O O22-broad -broad frequency modulationfrequency modulation
Cazzoli et al. JQSRT 2008 Cazzoli et al. JQSRT 2008
Cazzoli et al. JQSRT submitted Cazzoli et al. JQSRT submitted **Cazzoli et al. JQSRT in preparation Cazzoli et al. JQSRT in preparation
HH22O: THz pure rotational lines investigatedO: THz pure rotational lines investigated
JJ = 3 = 31,21,2 - 3 - 30,30,3** (1.097 THz) (1.097 THz) JJ = 1 = 11,11,1 - 0 - 00,00,0
(1.113 THz) (1.113 THz) JJ = 7 = 72,52,5 - 8 - 81,81,8
(1.147 THz) (1.147 THz) JJ = 3 = 31,21,2 - 2 - 22,12,1** (1.153 THz) (1.153 THz) JJ = 6 = 63,43,4 - 5 - 54,14,1** (1.158 THz) (1.158 THz) JJ = 3 = 32,12,1 - 3 - 31,21,2** (1.163 THz) (1.163 THz) JJ = 8 = 85,45,4 - 7 - 76,16,1
(1.168 THz) (1.168 THz) JJ = 7 = 74,44,4 - 6 - 65,15,1
(1.173 THz) (1.173 THz) JJ = 8 = 85,35,3 - 7 - 76,26,2
(1.191 THz) (1.191 THz) JJ = 6 = 63,33,3 - 5 - 54,24,2
(1.542 THz) (1.542 THz)
What was available for these lines? What was available for these lines?
- experimental values for 1- experimental values for 11,1 1,1 - 0- 00,00,0 (N (N22 && O O2 2 ) ) - calculated and/or extrapolated data for otherscalculated and/or extrapolated data for others - - experimental values for 1experimental values for 11,1 1,1 - 0- 00,00,0 (N (N22 && O O2 2 ) ) - calculated and/or extrapolated data for others calculated and/or extrapolated data for others
3) Experiment & Theory:3) Experiment & Theory: ResultsResults - H- H22O: which linesO: which lines - theo & exp results:- theo & exp results: previous exp dataprevious exp data
3) Experiment & Theory:3) Experiment & Theory: ResultsResults - H- H22O: which linesO: which lines - - theo & exp results:theo & exp results: previous exp dataprevious exp data
0 100 200 300 400 500 600 7000
2
4
6
8
10
12
14Self - broadening: 19.72(46) MHz/Torr
L (M
Hz)
H2O pressure (mTorr)
EXPTHEO
HITRAN
JJ = 1 = 11,11,1 – 0 – 00,00,0 transition of H transition of H22OO
T = 297 KT = 297 K
Cazzoli et al. JQSRT 2008Cazzoli et al. JQSRT 2008
0 100 200 300 400 500 600 7000.0
0.4
0.8
1.2
1.6
2.0
2.4
2.8
3.2
N
L (M
Hz)
N2 partial pressure (mTorr)
N2 - broadening:
4.38(15) MHz/Torr
Gasster et al JOSA B 1988
EXPTHEO
JJ = 1 = 11,11,1 – 0 – 00,00,0 transition of H transition of H22OO
T = 297 KT = 297 K
Cazzoli et al. JQSRT 2008Cazzoli et al. JQSRT 2008
0 100 200 300 400 500 600 7000.0
0.4
0.8
1.2
1.6
2.0
2.4
Gasster et al JOSA B 1988
O2 - broadening:
2.40(12) MHz/Torr
NL (M
Hz)
O2 partial pressure (mTorr)
EXP
THEO
JJ = 1 = 11,11,1 – 0 – 00,00,0 transition of H transition of H22OO
T = 297 KT = 297 K
Cazzoli et al. JQSRT 2008Cazzoli et al. JQSRT 2008
SelfSelf NN22 OO22 AirAir
297 K297 K ExpExp TheTheoo
ExpExp TheTheoo
ExpExp TheTheoo
ExpExp TheTheoo
This This workwork
19.72(4619.72(46))
19.819.8 4.38(154.38(15))
4.24.2 2.40(122.40(12))
2.52.5 3.96(133.96(13))
3.83.8
Gasster Gasster et al.et al.
3.67(103.67(10))
2.99(372.99(37))
3.53(8)3.53(8)
HITRANHITRAN 4.744.74 3.53(8)3.53(8)
JJ = 1 = 11,11,1 – 0 – 00,00,0 transition of H transition of H22OO
Improvements wrt old measurementsImprovements wrt old measurements
3) Experiment & Theory:3) Experiment & Theory: ResultsResults - H- H22O: which linesO: which lines - theo & exp results:- theo & exp results: HITRAN self broadHITRAN self broad
3) Experiment & Theory:3) Experiment & Theory: ResultsResults - H- H22O: which linesO: which lines - - theo & exp results:theo & exp results: HITRAN self broadHITRAN self broad
0 200 400 600 800 10000
2000
4000
6000
8000
10000
12000
14000
16000
18000
20000
L (k
Hz)
water pressure (mTorr)
Self-broadening: J = 72,5 - 8
1,8
17.96(34) MHz/Torr
HITRAN
EXP
THEO
Cazzoli et al. JQSRT submitted Cazzoli et al. JQSRT submitted
0 200 400 600 800 10000
2000
4000
6000
8000
10000
12000
14000
16000
Self-broadening: J = 85,4 - 7
6,1
11.12(26) MHz/Torr
L (
kHz)
water pressure (mTorr)
HITRAN
THEO
EXP
Cazzoli et al. JQSRT submitted Cazzoli et al. JQSRT submitted
0 200 400 600 800 10000
2000
4000
6000
8000
10000
12000
14000 Self-broadening: J = 74,4 - 6
5,1
11.98(27) MHz/Torr
HITRAN
THEO
EXP
water pressure (mTorr)
L (
kHz)
Cazzoli et al. JQSRT submitted Cazzoli et al. JQSRT submitted
0 200 400 600 800 10000
2000
4000
6000
8000
10000
12000
14000
16000
L (
kHz)
water pressure (mTorr)
Self-broadening: J = 63,4 - 5
4,1
14.97(8) MHz/Torr
HITRAN
THEO
EXP
Cazzoli et al. JQSRT in preparationCazzoli et al. JQSRT in preparation
0 200 400 600 800 10000
2000
4000
6000
8000
10000
12000
14000
16000
18000
20000
L (
kHz)
Self-broadening: J = 32,1 - 3
1,2
19.23(11) MHz/Torr
HITRAN
water pressure (mTorr)
THEO
EXP
Cazzoli et al. JQSRT in preparation Cazzoli et al. JQSRT in preparation
ExpExp TheoTheo
This workThis work JJ = 3 = 31,21,2 - 3 - 30,30,3 21.98(22)21.98(22) 21.5421.54
HITRANHITRAN 18.4018.40This workThis work JJ = 1 = 11,11,1 - 0 - 00,00,0 19.72(46)19.72(46) 19.819.8
HITRANHITRAN 4.744.74This workThis work JJ = 7 = 72,52,5 - 8 - 81,81,8 17.96(34)17.96(34) 17.9317.93
HITRANHITRAN 12.9312.93This workThis work JJ = 3 = 31,21,2 - 2 - 22,12,1 19.57(18)19.57(18) 21.2221.22
HITRANHITRAN 18.3318.33This workThis work JJ = 6 = 63,43,4 - 5 - 54,14,1 14.97(8)14.97(8) 16.2716.27
HITRANHITRAN 16.9416.94This workThis work JJ = 3 = 32,12,1 - 3 - 31,21,2 19.23(11)19.23(11) 19.8019.80
HITRANHITRAN 18.4018.40This workThis work JJ = 8 = 85,45,4 - 7 - 76,16,1 11.12(26)11.12(26) 11.3311.33
HITRANHITRAN 15.1615.16This workThis work JJ = 7 = 74,44,4 - 6 - 65,15,1 11.98(27)11.98(27) 13.0313.03
HITRANHITRAN 16.6916.69This workThis work JJ = 8 = 85,35,3 - 7 - 76,26,2 11.66(8)11.66(8) 11.8811.88
HITRANHITRAN 15.1615.16This workThis work JJ = 6 = 63,33,3 - 5 - 54,24,2 17.5617.56
HITRANHITRAN 16.9416.94
What’s the problem? What’s the problem?
SELF-broadeningSELF-broadening
COMPARISONCOMPARISON: : semiclassical calc. (SC) vs HITRAN (assumption*) valuessemiclassical calc. (SC) vs HITRAN (assumption*) values
**dependence of the broadening parameter on dependence of the broadening parameter on J”J”
COMPARISONCOMPARISON: : semiclassical calculations (SC) vs HITRAN (exp*) valuessemiclassical calculations (SC) vs HITRAN (exp*) values
**IR lines: 600-1000 cmIR lines: 600-1000 cm-1-1 (R. A. Toth) (R. A. Toth)
COMPARISONCOMPARISON: : semiclassical calculations (SC) vs EXP* valuessemiclassical calculations (SC) vs EXP* values
**Markov 1994, Cazzoli et al. 2007, Cazzoli et al. 2008 Markov 1994, Cazzoli et al. 2007, Cazzoli et al. 2008
SuggestionSuggestion: : Make use of calculated values when no Make use of calculated values when no reliable experimental data are availablereliable experimental data are available
HITRAN ref. # lines Mean %error #lines with %err > 25%
3 98 8.3 1013 6 43.3 415 15 37.3 823 1 3.7 030 3 6.8 031 2 39.6 236 1 24.7 050 43 14.7 751 1333 37.5 59552 1 76.6 153 3 24.1 1
Ref. 51: Averaged values as a function of Ref. 51: Averaged values as a function of JJ””
3) Experiment & Theory:3) Experiment & Theory: ResultsResults - H- H22O: which linesO: which lines - theo & exp results:- theo & exp results: NN22, O, O22 & air broad & air broad
3) Experiment & Theory:3) Experiment & Theory: ResultsResults - H- H22O: which linesO: which lines - - theo & exp results:theo & exp results: NN22, O, O22 & air broad & air broad
0 200 400 600 800 10000
400
800
1200
1600
2000
2400
2800
3200 N2-broadening: J = 7
4,4 - 6
5,1
3.127(34) MHz/Torr
NL (
kHz)
nitrogen partial pressure (mTorr)
THEO
EXP
Cazzoli et al. JQSRT submitted Cazzoli et al. JQSRT submitted
0 200 400 600 800 10000
200
400
600
800
1000
1200
1400
1600
1800
2000
2200 O2-broadening: J = 6
3,3 - 5
4,2
1.967(66) MHz/Torr
NL (
kHz)
oxygen partial pressure (mTorr)
EXP
THEO
Cazzoli et al. JQSRT submitted Cazzoli et al. JQSRT submitted
ExpExp TheoTheoThis workThis work JJ = 3 = 31,21,2 - 3 - 30,30,3 3.970(82)3.970(82) 4.004.00
HITRANHITRAN 4.134.13This workThis work JJ = 1 = 11,11,1 - 0 - 00,00,0 3.96(13)3.96(13) 3.83.8
HITRANHITRAN 3.53(8)3.53(8) This workThis work JJ = 7 = 72,52,5 - 8 - 81,81,8 3.508(20)3.508(20) 3.133.13
HITRANHITRAN 3.243.24This workThis work JJ = 3 = 31,21,2 - 2 - 22,12,1 3.935(75)3.935(75) 3.773.77
HITRANHITRAN 3.653.65This workThis work JJ = 6 = 63,43,4 - 5 - 54,14,1 2.911(60)2.911(60) 2.802.80
HITRANHITRAN 2.992.99This workThis work JJ = 3 = 32,12,1 - 3 - 31,21,2 3.857(57)3.857(57) 3.773.77
HITRANHITRAN 3.933.93This workThis work JJ = 8 = 85,45,4 - 7 - 76,16,1 2.287(66)2.287(66) 2.072.07
HITRANHITRAN 2.182.18This workThis work JJ = 7 = 74,44,4 - 6 - 65,15,1 2.765(34)2.765(34) 2.422.42
HITRANHITRAN 2.592.59This workThis work JJ = 8 = 85,35,3 - 7 - 76,26,2 2.462(24)2.462(24) 2.182.18
HITRANHITRAN 2.272.27This workThis work JJ = 6 = 63,33,3 - 5 - 54,24,2 3.805(72)3.805(72) 3.283.28
HITRANHITRAN 3.323.32
Good agreement! Good agreement!
AIR-broadeningAIR-broadening
3) Experiment & Theory:3) Experiment & Theory: ResultsResults - H- H22O: which linesO: which lines - theo & exp results:- theo & exp results: shift & SD paramshift & SD param
3) Experiment & Theory:3) Experiment & Theory: ResultsResults - H- H22O: which linesO: which lines - - theo & exp results:theo & exp results: shift & SD paramshift & SD param
100 200 300 400 500 600 70041.0
41.2
41.4
41.6
41.8
42.0
42.2
42.4
42.6
42.8
43.0
43.2Self - shift: J = 1
1,1 - 0
0,0
-2.52(41) MHz/TorrFre
quency
(M
Hz)
H2O pressure (mTorr)
EXP
THEO
Cazzoli et al. JQSRT 2008 Cazzoli et al. JQSRT 2008
0 100 200 300 400 500 600 700 800
620.5
620.6
620.7
620.8
620.9
621.0
621.1
621.2
621.3
621.4
Self - shift: J = 72,5 - 8
1,8
-1.00(11) MHz/TorrFre
quency
(M
Hz)
water pressure (mTorr)
EXPTHEO
Cazzoli et al. JQSRT submitted Cazzoli et al. JQSRT submitted
0 200 400 600 800 100058.45
58.50
58.55
58.60
58.65
58.70
58.75 Nitrogen - shift: J = 85,4 - 7
6,1
0.199(10) MHz/TorrFre
quency
(M
Hz)
nitrogen partial pressure (mTorr)
THEO
EXP
Cazzoli et al. JQSRT submitted Cazzoli et al. JQSRT submitted
0 200 400 600 800 10000
100
200
300
400
500
600
700
800 N2 - relax (J =31,2-2
2,1): SD parameter
0.638(32) MHz/Torr 2
(k
Hz)
nitrogen partial pressure (mTorr)
EXP THEO
Cazzoli et al. JQSRT in preparation Cazzoli et al. JQSRT in preparation
ConclusionsConclusions
10 pure rotational THz water lines10 pure rotational THz water lines have have been experimentally and theoretically been experimentally and theoretically investigated investigated
GoodGood agreement agreement between experiment between experiment
and SC calculations and SC calculations
UpdateUpdate for HITRAN self broadening for HITRAN self broadening parameters is suggested parameters is suggested
Rather accurateRather accurate experimental results experimental results have been obtainedhave been obtained
temperaturetemperatureexponent exponent nn
n
TT
TXTX
0
00 )()(
Least-square fit:Least-square fit: ln(X/Xln(X/X00) = ) = n n ln(Tln(T00/T)/T)
TEMPERATURE DEPENDENCETEMPERATURE DEPENDENCE
TEMPERATURE DEPENDENCETEMPERATURE DEPENDENCE
Laboratory of Millimetre-waveLaboratory of Millimetre-wave
Spectroscopy of BolognaSpectroscopy of BolognaPRAHA 2006PRAHA 2006
temperaturetemperatureexponent exponent nn
n
TT
TXTX
000 )()(
Least-square fit:Least-square fit: ln(X/Xln(X/X00) = ) = n n ln(Tln(T00/T)/T)
0.0 0.1 0.2 0.3 0.4 0.5-0.05
0.00
0.05
0.10
0.15
0.20
0.25
0.30
O3: 301.8 GHz
O2-broadening
n = 0.684(14)
ln(/ 0)
ln(T0/T)