Rejuvenated spectroscopy of “simple” diatomic molecules in HITRAN

Iouli Gordon, Laurence Rothman Halides: G. Li, P. Bernath, R. Le Roy, J. Coxon, P. Hajigeorgiou

ASA/HITRAN meeting, Reims, France. August 31, 2012

Oxygen: G. Toon, C. Mackie, A. Campargue, S. Kassi, O. Leshchishina

“Victims” of simplicity • First realized in 1880s by Knut Ångström through

different appearance of CO and CO2 spectra

• In the first 100 years literally hundreds of experimental and theoretical papers on each of the simplest diatomics like CO, HF, HCl and OH

• More recent papers concentrate mostly on ultra-high precision measurements of individual lines and studies of line-shape phenomena

• Spectroscopy of these molecules was considered to be well established and parameters of diatomic molecules in major databases like HITRAN were not revised in decades (with a few exceptions).

OH Example

•Parameters in HITRAN1996-2004 are based on constants from Melen et al (1995) for v=0-3 and from Abrams et al (1994) for v>3. •A number of more recent works have noted that Abrams et al constants do not reproduce their own data. •In 2009 Bernath and Colin refitted Abrams et al data supplemented with all other high-resolution measurements including extensive solar spectrum from ATMOS.

OH Example

010

2030

40

0

10

20

30

40

02

46

810

v"

HIT0

4-HI

T08,

cm

-1

J"

Diatomics in HITRAN

NO+ (NO cation)

N2 (nitrogen)

BandsMolecule

ClO (chlorine monoxide)

HI(hydrogen iodide)

HBr(hydrogen bromide)

HCl(hydrogen chloride)

HF(hydrogen fluoride)

OH (hydroxyl radical)

NO (nitric oxide)

3O2 (oxygen)

0-0, 1-1, 1-0, 2-1, 2-0, 3-1, 3-0, 4-1CO(carbon monoxide)

# ofIsotopo-logues

6

1 3g ga X −∆ ← Σ3 3

g gX X− −Σ ← Σ 1 3g gb X− −Σ ← Σ

3 2 2i iX XΠ Π← 0,1,2,3v∆ = 0,1,2,.....v =′′

3 2 2i iX XΠ Π← 0,1,2,3v∆ = 0,1,2,.....v =′′

1

2

2

1

2

1

1

0-0, 1-1, 1-0, 2-1, 2-0, 3-0

1-0

0-0, 1-1, 1-0, 2-1, 2-0, 3-1, 3-0, 4-0

0-0, 1-1, 1-0, 2-1, 2-0, 3-1, 3-0, 4-1, 4-0

2 2i iX XΠ Π← 0-0, 1-0

0-0, 1-1, 1-0, 2-1, 2-0, 3-1, 3-0, 4-0, 5-0

1-0, 2-1, 3-2, 4-3, 5-4, 6-5

Traditional method of constructing semi-empirical DMF for diatomic molecules

Step 1:

Herman-Wallis fitting of the measurements in the individual vibrational bands

...),1(|)0(||"0)('| 220

2 +++= mDmCRJxMJ υυυυ

𝑆𝑆 = 𝐼𝐼𝑎𝑎8𝜋𝜋3

3ℎ𝑐𝑐𝑒𝑒−𝑐𝑐2𝐸𝐸" 𝑇𝑇0⁄ �1 − 𝑒𝑒−𝑐𝑐2𝑣𝑣 𝑇𝑇0⁄ �𝑔𝑔𝑖𝑖𝑔𝑔𝑠𝑠|𝑚𝑚|𝑹𝑹12 × 10−36

Herman-Wallis fitting

...),1(|)0(||"0)('| 220

2 +++= mDmCRJxMJ υυυυ

Traditional method

Step 1:

Herman-Wallis fitting of the measurements in the individual vibrational bands

Step 2:

Rotationless squares of the transition dipoles are fitted to the polynomial expressions

,)( ∑=i

ii xMrM

e

er

rrx −=

1

' ( ) 0 " ' 0 "n

ii

ivJ M x J M vJ x J

=

= ∑ , J’=J”=0

• Disregard of the rotational information • Dependence on the amount of data within the same

vibrational band • Disregard of the experimental uncertainties

Disadvantages of the traditional method and suggested alternatives

Kiriyama F, Rao BS, Nangia VK. Electric dipole moment function of H35Cl. JQSRT 2001;69:35-40, suggested to fit all of the intensities to DMF.

1

' ( ) 0 " ' 0 "n

ii

ivJ M x J M vJ x J

=

= ∑

Flaws in Kiriyama et al. approach • Still carried out the Hermann-Wallis fit to “smooth” experimental data • Dependence on the amount and relative quality of the data within the

same vibrational band • Disregarded the experimental uncertainties • Incorrect treatment of isotopic abundance when treating experimental

data from Pine et al (1-0) and Toth et al (2-0)

Proposed approach

• Calculate expectation values using RKR or empirical potential

• Do a least squares fit to obtain Mi coefficients. Every ro-vibrational measurement is included with appropriate weight

1

' ( ) 0 " ' 0 "n

ii

ivJ M x J M vJ x J

=

= ∑

Input parameters 1-0 • Pine AS, Fried A, Elkins JW, J Mol Spectrosc 1985;109:30-45. 2-0 • a) Toth RA, Hunt RH, Plyler EK, J Mol Spectrosc 1970;35:110-26. b) De Rosa M, Nardini C, Piccolo C, Corsi C, D'Amato F, Appl Phys B:

Lasers Opt 2001;72:245-8. c) Ortwein P, Woiwode W, Wagner S, Gisi M, Ebert V. , Appl Phys B:

Lasers Opt 2010;100:341-7. 3-0 • a) Ogilvie JF, Lee Y-P, Chem Phys Lett 1989;159:239-43. b) Stanton AC, Silver JA, Appl Opt 1988;27:5009-15. 4-0 to 7-0 • a) Gelfand J, Zughul M, Rabitz H, Han CJ, JQSRT 1981;26:303-5. b) Reddy KV, J Mol Spectrosc 1980;82:127-37.

Obtained dipole moment function

2-0 HCl line intensities

-8 -6 -4 -2 0 2 4 6 8 10 12-10-8-6-4-202468

101214

Exp. [(Toth et al.) vs present study Calc. (Ogilvie&Lee) vs present study HITRAN vs present study Exp. (de Rosa et al.)vs present study Exp. [Ortwein et al.) vs present study

Perc

enta

ge d

iffer

ence

s of

line

inte

nsitie

s / %

m

-7%

3-0 HCl line intensities

-8 -6 -4 -2 0 2 4 6 8 10 12-30-25-20-15-10-505

1015202530

Pe

rcen

tage

diff

eren

ces

of lin

e in

tens

ities

/ % Present study vs exp. (O&L) Calc. (O&L) vs exp. (O&L) HITRAN vs exp. (O&L) Exp. (Stanton et al.) vs exp. (O&L)

m

-17.5%

O&L- Ogilvie JF, Lee Y-P, Chem Phys Lett 1989;159:239-43.

5-0 HCl line intensities

-8 -6 -4 -2 0 2 4 6 8 10 12

-20

-10

0

10

20

30

40

50

Perc

enta

ge d

iffer

ence

s of

line

inte

nsitie

s / % Present study vs exp. (Gelfand et al)

Calc. (Ogilvie&Lee )vs exp. (Gelfand et al) HITRAN vs exp. (Gelfand et al) Exp. Reddy vs exp. (Gelfand et al)

m

Perc

ent d

iffer

ence

in H

F in

tens

ities

HF line intensities

Perc

ent d

iffer

ence

in H

F in

tens

ities

HF line intensities

Evaluation, improvement and

extension of oxygen spectroscopic

parameters

Lowest electronic states of O2

b 1Σ+

a 1∆g

X 3Σg -

M1- Magnetic dipole

E2- Electric quadrupole

M1,

E2

M1,

E2

E2 M1>> E2

F1 (J=N+S)

F2 (J=N+S-1)

F3 (J=N-S)

⟩Σ−⟩Σ=⟩

⟩Σ=⟩

⟩Σ+⟩Σ=⟩

±

±

±

03

13

3

13

2

03

13

1

|||

||

|||

JJ

JJ

scFF

csF1.27 µm

0.76 µm g

Old JPL and current HITRAN MW intensities comparison

New JPL and current HITRAN MW intensities comparison

Quadrupole transitions in the 1.27 µm band

8

9 10

8

9

10

11

7

6

12

e

f

e

f

f

e

e

e f

e

∆J=±2 ∆J=±1 ∆J=0

T(9)

S(10

)

R(9)

S(8)

P(9)

O(1

0)

S(9)

S(9)

O(9

)O(9

)

N(9

)O(8

)

S(9)

R(10

)

R(9)

R(9)

P(9)

P(9)

O(9

)P(8

)

R(9)

Q(1

0)

Q(9

)Q(9

)

P(9)

Q(8

)

J

N=9 F1 F2

F3 Q

(9)R

(8)

Q(9

)P(1

0)

Notation of branches:

ΔN(N’’)ΔJ(J’’)

⟩Σ−⟩Σ=⟩

⟩Σ=⟩

⟩Σ+⟩Σ=⟩

±

±

±

03

13

3

13

2

03

13

1

|||

||

|||

JJ

JJ

scFF

csF

Gordon I.E. , S. Kassi, A. Campargue, and G.C. Toon, JQSRT 111, 1174-1183 (2010).

447-

m W

LEF

tow

er

FTS near Tall Tower in Park Falls WI

Total Column Carbon Observing Network (TCCON)

Comparison between HITRAN and Ground-based FTS observations for Oxygen B-band

Experiment by G. Toon, at Wisconsin tower site

14400 14450 14500 14550 Wavenumber (cm-1)

RMS = 2.176%

Recorded 22 Dec 2004

Parameter (cm-1) This work Albritton et al a Cheah et al b Phillips et al c Naus et al d

T1 14526.9896(12) 14526.9909(17) 14525.65553(26) 14526.9976(12)

B1 1.3729553(72) 1.372982(10) 1.3729659(22) 1.372951(18)

D1 5.3960(93) ×10-6 5.418(10) ×10-6 5.4086(42) ×10-6 5.397(50) ×10-6

T2 15903.7479(27) 15903.7509(16) 15902.4251(32) 15903.748(3)

B2 1.354630(23) 1.354609(11) 1.354644(38) 1.35463(2)

D2 5.484(36) ×10-6

Number of lines used in this

work per band

MW: 85; Raman: 94; b1Σg+ (v=1) − a1Δg(v=0): 29; a1Δg − X 3Σg− : 199;

b1Σg+ (v=1) − X 3Σg− (v=0): 72; b1Σg+ (v=2) − X 3Σg− (v=0): 49

Spectroscopic parameters of the v = 1 and 2 levels of the b1Σg

+ state of 16O2

a. Albritton DL, Harrop WJ, Schmeltekopf AL, Zare RN, J Mol Spectrosc 1973;46:103-18 b. Cheah S-L, Lee Y-P, Ogilvie JF, JQSRT 2000;64:467-82 c. Phillips AJ, Peters F, Hamilton PA, J Mol Spectrosc 1997;184:162-6 d. Naus H, Navaian K, Ubachs W, Spectrochimica Acta Part A 1999;55:1255-62

Comparison between New Analysis and Ground-based FTS observations for Oxygen B-band

Comparison between HITRAN and Ground-based FTS observations for Oxygen B-band

Experiment by G. Toon, at Wisconsin tower site

14400 14450 14500 14550 Wavenumber (cm-1)

RMS = 2.176%

Recorded 22 Dec 2004

I.E. Gordon, L.S. Rothman, and G. C. Toon “Revision of spectral parameters for the B- andγ-bands of oxygen and their validation against atmospheric spectra,” JQSRT, 112, 2310-2322 (2011). G. Li, I.E. Gordon, P.F. Bernath, and L.S. Rothman, “Direct fit of experimental ro-vibrational intensities to the dipole moment function: Application to HCl,” JQSRT, 112, 1543-1550(2011). O. Leshchishina, S. Kassi, I.E. Gordon, S.Yu, and A. Campargue, “The band of 16O17O, 17O18O and 17O2 by high sensitivity CRDS near 1.27 mm.,” JQSRT, 112, 1257-1265 (2011). S. Kassi, O. Leshchishina, I.E. Gordon, S.Yu, and A. Campargue, “Hyperfine structure of the a1Δg - X 3Σg

- transitions of 16O17O, 17O18O and 17O2 by CRDS at 80K,” Chem. Phys. Lett., 502, 37-41 (2011). O. Leshchishina, S. Kassi, I.E. Gordon, L.S. Rothman, L. Wang, and A. Campargue, “High sensitivity CRDS of the a1Δg - X 3Σg

- band of oxygen near 1.27 μm: extended observations, quadrupole transitions, hot bands and minor isotopologues,” JQSRT, 111, 2236-2245 (2010). I.E. Gordon, S. Kassi, A. Campargue, and G.C. Toon, “First identification of the a1Δg - X 3Σg

- electric quadrupole transitions of oxygen in solar and laboratory spectra,” JQSRT 111, 1174-1183 (2010).

Publications

Conclusions

There is still significant room for spectroscopic research of diatomic molecules of atmospheric and planetary interest Analyses of the data has to be carried out as globally as possible Publications should include, in order of preference, experimental line lists, range of measured transitions, properly explained equations (like Hamiltonians), spectroscopic constants (these constants should be tested if they can reproduce your data)

4-0 HCl line intensities

-8 -6 -4 -2 0 2 4 6 8 10-20

-15

-10

-5

0

5

10

15

20Pe

rcen

tage

diff

eren

ces

of lin

e in

tens

ities

/ % Present study vs exp. (Gelfand et al.) Calc. (Ogilvie&Lee)) vs exp. (Gelfand et al.) HITRAN vs exp. (Gelfand et al.)

m

7-0 HCl line intensities

-6 -4 -2 0 2 4 6 8 10-25

-20

-15

-10

-5

0

5

10

15

20

25

Perc

enta

ge d

iffer

ence

s of

line

inte

nsitie

s / %

Present study vs exp. (Gelfand et al.) Calc. Ogilvie&Lee vs exp. (Gelfand et al.)

m

2700 2800 2900 3000 5500 5600 5700 5800-2-101234

8200 8300 8400 10700 10800 10900 11000

-6-3036

13200 13300 13400 15600 15700 15800-10-505

10

17850 17900 17950 18000 18050 18100-505

10

Calculations using RKR potential vs experimental values

Calculations using Coxon&Hajigeorgiou potentiala vs experimental values

Wavenumber / cm-1

Per

cent

age

diffe

renc

es o

f tra

nsitio

n di

pole

mom

ent

/ %

RKR versus “exact” potential