**[INFRARED LABORATORY SPECTROSCOPY for AIRS, TES and
HIRDLS]{.underline}**

**NASA Research Announcement 00‑OES‑03**

**Principal Investigator: [LINDA R. BROWN ]{.underline}**

**Department: [Earth and Space Sciences (division 32) ]{.underline}**

**Institution: [Jet Propulsion Laboratory M. S. 183-601 ]{.underline}**

**Street/PO Box: [4800 Oak Grove Dr. ]{.underline}**

**City: [Pasadena]{.underline} State: [CA]{.underline} Country:
[USA]{.underline} Zip: [91109-8099 ]{.underline}**

**E‑mail [Linda.r.brown@jpl.nasa.gov ]{.underline}**

**Telephone: [818-354-2940]{.underline} Fax: [818-354-5148
]{.underline}**

**[CO‑INVESTIGATORS:]{.underline}**

**[Name]{.underline} [Institution]{.underline} [Email
Address]{.underline} [Address]{.underline} [Telephone]{.underline}**

R. A. Toth JPL Robert.toth@jpl.nasa.gov Same as PI 18 354‑6860

G. Toon JPL toon@mark4sun.jpl.nasa.gov Same as PI 818 354‑8259

B. Sen JPL Sen@caesar.jpl.nasa.gov Same as PI 818 354‑1165

V. M. Devi College of m.d.venkataraman 757 864‑5521

> William&Mary \@larc.nasa.gov Williamsburg, VA 23187‑8795

D. C. Benner College of [dc.benner@lwm.edu](mailto:dc.benner@lwm@edu) PO
8795, Physics 757 221‑3531

> William&Mary Williamsburg, VA 23187‑8795

M. A. H. Smith LARC m.a.h.smith@larc.nasa.gov MS 401A, LARC, 757
864‑2701

**Summary**

This laboratory study updated molecular line parameters of H~2~O, NO~2~,
CH~4~ and CO in the 2005 **HITRAN** compilation for **AIRS**, **TES**
and **HIRDLS,** as well as for **MIPAS, IASI** and **ACE**. We evaluated
available line positions, intensities and line shape parameters at room
temperature for H~2~O and NO~2~ and combined them with our new line
shape measurements. The data sets were written into **HITRAN** format
for water transitions between 600 and 2100 cm^-1^ and NO~2~ transitions
between 1560 and 1660 cm^-1^. We also merged ongoing measurements of
line intensities and line shape parameters (obtained through other
contracts) for CH~4~ transitions between 1000 and 3200 cm^-1^ and CO
transitions of the 1 - 0 fundamental band near 2150 cm^-1^. We achieved
our goal to incorporate accurate line shape parameters into the
**HITRAN** database for EOS tropospheric retrievals of these four
molecular species. These data were also included in the customized
databases for **TES, GEISA/IASI** and **MIPAS**. Final results are
summarized in Table 1.

Our laboratory study characterized the temperature dependence of
air‑broadened H~2~O and air-broadened NO~2~ line shape coefficients
(widths and pressure-induced shifts in positions) for which there were
scant measurements. For H~2~O, some 300 air‑broadened widths and shifts
at temperatures between 242 and 388 K were measured between 670 and 2100
cm^-1^ in laboratory spectra recorded with the FTS at Kitt Peak. **In
addition, line mixing between pairs of water transitions was observed
for the first time.** Finally, an additional study was undertaken to
investigate line mixing in the
![](media/image1.png){width="0.10416666666666667in"
height="0.10416666666666667in"}~4~ Q branch of methane at 1300 cm^-1^ to
support **TES** analysis; an oral presentation was given at the 2005
Symposium on Molecular Spectroscopy in Columbus, OH, and a manuscript is
being prepared.

**TABLE 1 LABORATORY STUDIES for AQUA (FY2001 - FY2005)**

+------+-----+-------------------------+------------------------------+
| **S  | **λ | **Type of Analysis and  | **Publications (Ref. #,      |
| peci | μ   | Results**               | first author)**              |
| es** | m** |                         |                              |
+------+-----+-------------------------+------------------------------+
| *    | 5 - | New lab measurements of | **1.**Toth, **O~2~ +water**, |
| *H~2 | 16  | hot air-broadened water | J. Mol. Spectrosc. (2003).   |
| ~O** |     | to obtain temperature   |                              |
|      |     | dependence of widths    | **13.**Toth, **hot water     |
|      |     | and shifts Analyze      | widths**, (submitted to J.   |
|      |     | widths, shifts temper.  | Quant. Spectrosc. Rad.       |
|      |     | dependence data         | Tranfer).                    |
|      |     |                         |                              |
|      |     | Merge all new           | **2.** Flaud,                |
|      |     | spectroscopy of widths, | **MIPAS,**Atmos Oceanic Opt. |
|      |     | shifts, temperature     | (2003).                      |
|      |     | dependences,            |                              |
|      |     | intensities from this   | **11.**Rothman **HITRAN,**   |
|      |     | and other studies to    | to J. Quant. Spectrosc. Rad. |
|      |     | update HITRAN database  | Tranfer (2005)               |
|      |     |                         |                              |
|      |     | First observation of    | **12**. Clough,. **TES**,    |
|      |     | line mixing in water    | submitted IEEE               |
|      |     | spectra                 |                              |
|      |     |                         | **9.** Brown. **H~2~O line   |
|      |     |                         | mixing**, J. Mol. Structure  |
|      |     |                         | (2005)                       |
+------+-----+-------------------------+------------------------------+
| *    | 6.2 | Measure and analyze hot | **6.** Benner, **NO~2~       |
| *NO~ |     | and cold air-broadened  | Pressure broadening**, J.    |
| 2~** |     | line widths and their   | Mol. Spectrosc. (2004)       |
|      |     | temperature dependences |                              |
|      |     | of v~3~ band            | **11.** L.S. Rothman,        |
|      |     |                         | **HITRAN,** JQSRT (2005)     |
|      |     | Merge all new           |                              |
|      |     | spectroscopy from this  | **8.** Jacquinet-Husson      |
|      |     | and other studies to    | **GEISA/IASI,** JQSRT (2005) |
|      |     | update HITRAN database  |                              |
+------+-----+-------------------------+------------------------------+
| *    | 3 - | Merge all new           | **4.** Brown, **CH~4~ in     |
| *CH~ | 10  | spectroscopy from other | databases** JQSRT (2003 )    |
| 4~** |     | studies involving       |                              |
|      |     | intensities of weak     | **11.** Rothman, **HITRAN    |
|      |     | features and line       | 2004,** JQSRT (2005)         |
|      |     | shapes to update HITRAN |                              |
|      |     | database                | **8.** Jacquinet-Husson,     |
|      |     |                         | **GEISA,** JQSRT (2005)      |
|      |     | Self- and               |                              |
|      |     | air-broadening in weak  | **10.** **& 14**. A.         |
|      |     | bands                   | Predoi-Cross, **CH~4~        |
|      |     |                         | pressure broadening** at 2.3 |
|      |     |                         | µm, J. Mol. Spectrosc.       |
|      |     |                         | (2005) and Submitted         |
+------+-----+-------------------------+------------------------------+
| **   | 4.6 | Merge all new           | **5**. Smith, 1 -- 0 band of |
| CO** |     | spectroscopy from other | CO (HITRAN)                  |
|      |     | studies involving       |                              |
|      |     | intensities and line    | **11**. Rothman, **HITRAN,** |
|      |     | shapes to update HITRAN | JQSRT (2005)                 |
|      |     | database                |                              |
|      |     |                         | **8.**                       |
|      |     | Speed dependent line    | Jacquinet-Husson,**GEISA,**  |
|      |     | profiles with line      | JQSRT (2005)                 |
|      |     | mixing in the 2 - 0     |                              |
|      |     | band of CO              | **6.** Brault, **Line        |
|      |     |                         | shapes**, J. Mol. Spectrosc. |
|      |     |                         | (2004)                       |
+------+-----+-------------------------+------------------------------+

For NO~2~ at 6 μm, the retrieval software was improved to apply
constraints for the nearly- degenerate spin transitions so that
air-broadening coefficients could be accurately measured in complex high
resolution spectra. Some 1000 air‑ broadened widths and shifts were
measured at temperatures between 210 and 400 K. New empirical
expressions for calculating broadening coefficients of NO~2~ were
discovered. These data were analyzed to form empirical lists of widths
and shift coefficients as a function of rotational quantum numbers.
These formulas were then successively applied to the water molecule and
reproduced air-broadened H~2~O line widths more accurately than existing
quantum mechanical models. These were merged with published room
temperature results for air‑ and self‑broadened widths, line positions
and intensities to obtain complete and accurate new compilations for
H~2~O and NO~2~ in the spectral intervals critical to **AIRS**, **TES**
and **HIRDLS**.

For methane and carbon monoxide, laboratory studies were undertaken and
combined with new published results from other investigators. The
initial improvements appeared in the **HITRAN** 2004 compilation of
molecular parameters band, and additional information will be available
for the next version of **HITRAN**.

Self- and air- broadened widths of methane at room temperature were
characterized through empirical measurements of weak bands in the
**MOPITT** region; it was demonstrated that the variation of widths for
complex combination and overtone was much different from the pattern of
coefficients seen in the simple fundamentals. It was also seen that
averaged values of pressure shifts were proportional to the value of the
band centers. Empirical look-up tables of broadening coefficients were
formed which can be applied to infrared methane bands and also to guide
the development of empirical models.

For CO, measurements from other studies were evaluated and used to
create updated parameters for **TES** and for the **HITRAN** and
**GEISA** databases. An important study of the 2 -- 0 band of CO
demonstrated the importance of non-Voigt line shapes if highly accurate
intensities and widths are to be retrieved from laboratory spectra. In
this study, speed dependent profiles combined with line mixing between P
and R branch transitions were observed for CO.

**Resulting Publications (supported in part or in total by this task)**

1\. R. A Toth and L. R. Brown, Oxygen broadening parameters of water
vapor: 1212-2136 cm^-1^, J. Mol. Spectrosc. 218, 135-150 (2003).

2\. J.-M Flaud, C. Piccolo, B. Carli, A. Perrin, L. H. Coudert, J.-L.
Teffo and L. R. Brown, Molecular line parameters for the MIPAS
(Michelson Interferometer for Passive Atmospheric Sounding) experiment,
Atmospheric and Oceanic Optics 16, 172-182 (2003). .

3**.** L.S. Rothman, A. Barbe, D.C. Benner, L.R. Brown, C. Camy-Peyret,
M.R. Carleer, K. Chance, C. Clerbaux, V. Dana, V.M. Devi, A. Fayt, J.-M.
Flaud, R.R. Gamache, A. Goldman, D. Jacquemart, K.W. Jucks, W.J.
Lafferty, J.-Y. Mandin, S.T. Massie, V.Nemtchinov, D.A. Newnham, A.
Perrin, C.P. Rinsland, J. Schroeder, K.M. Smith, M.A.H. Smith, K. Tang,
R.A. Toth, J. Vander Auwera, P. Varanasi and K. Yoshino, The HITRAN
Molecular Spectroscopic Database: Edition of 2000 Including Updates
through 2001, *J. Quant. Spectrosc. Rad. Transfer* **82**, 5-44 (2003).

4**.** L. R. Brown, D. Chris Benner, J.P. Champion, V.M. Devi, L.
Fejard, R.R. Gamache, T. Gabard, J.C. Hilico, B. Lavorel, M. Loete, G.
Ch. Mellau, A. Nikitin, A. S. Pine, A. Predoi-Cross, C. P. Rinsland, O.
Robert, R. L. Sams, M.A.H. Smith, S. A.Tashkun, and Vl. G. Tyuterev,
Methane line parameters in **HITRAN**, *J. Quant. Spectrosc. Rad.
Transfer* **82**, 219-238 (2003).

5\. M. A. H. Smith, L. R. Brown, V. Malathy Devi, T. J. Pittman, CO
Broadening and Shift Parameters for **TES**, 8^th^ HITRAN Conference,
June 2004, Cambridge, MA.

6\. Brault, J.W. , Brown, L.R., Chackerian, C., Jr., Freedman, R.,
Predoi-Cross, A. and Pine, A.S. ,Self-broadened CO line shapes in the
v=2-0 band, J. Mol. Spectrosc. **222**,220-239 (2003).

7\. D. Chris Benner, T. A. Blake, L. R. Brown, V. Malathy Devi, M.A.H.
Smith and R. A. Toth, Air-broadening parameters in the v~3~ band of
^1**4**^**N^16^O~2~** using a multispectrum fitting technique, J. Mol.
Spectrosc. 228, 593-619 (2004).

8\. N. Jacquinet-Husson, N.A. Scott, A. Chédin, K. Garceran, R. Armante,
A.A. Chursin, A. Barbe, M. Birk, L.R. Brown, C. Camy-Peyret, C. Claveau,
C. Clerbauxg, P.F. Coheur, V. Dana, L. Daumont, M.R. Debacker-Barilly,
J.M. Flaud, A. Goldman, A. Hamdouni, M. Hess, K. Köpke, J.Y. Mandin, S.
Massie, S. Mikhailenko, V. Nemtchinov, A. Nikitin, D. Newnham, A.
Perrin, L. Régalia-Jarlot, A. Rublev, F. Schreier, L. Schult, K.M.
Smith, S.A. Tashkun, J.L. Teffo, R.A. Toth, Vl.G. Tyuterev, J.
Vander-Auwera, P. Varanasi, G. Wagner, The 2003 Edition Of The
**GEISA/IASI** Spectroscopic Database, JQSRT 95, 429-467 (2005).

9\. L. R. Brown, D. Chris Benner, V. Malathy Devi, M.A.H. Smith and R.
A. Toth, **Line mixing** in self- and foreign-broadened **water** vapor
at 6 μm, J. Mol. Structure 742, 111-122 (2005).

10\. A. Predoi-Cross, L. R. Brown, V.M. Devi, and D. C. Benner,
Multispectrum analysis of self-broadening and pressure-shifting
coefficients of **^12^CH~4~** from 4100 to 4635 cm^-1^, J. Mol.

Spectrosc. 232, 231-246 (2005).

11\. L.S. Rothman, D. Jacquemart, A. Barbe, D.C. Benner, M. Birk, L.R.
Brown, M.R. Carleer, C. Chackerian, Jr, K. Chance, V. Dana, V.M. Devi,
J.‑M. Flaud, R.R. Gamache, A. Goldman, J.-M. Hartmann, K.W. Jucks,
A.G. Maki, J.‑Y. Mandin, S. Massie, J. Orphal, A. Perrin, C.P. Rinsland,
M.A.H. Smith, R.A. Toth, J. Vander Auwera, P. Varanasi, G. Wagner, The
**HITRAN** 2004 Molecular Spectroscopic Database JQSRT 92(2) 139-207
(2005).

12\. S. A. Clough, M. W. Shepard, J. Worden, P. D. Brown, H. M. Worden,
M. Luo, C. D. Rodgers, C. P. Rinsland, A. Goldman, L. R. Brown, A.
Eldering, S. Sund-Kulawik, K. E. Cady,Pereira,M. C. Lampel, G. Osterman
and R. Beer, Forward Model and Jacobians for **T**ropospheric
**E**mission **S**pectrometer Retrievals, (accepted to IEEE AURA special
issue).

13\. R. A. Toth, L. R. Brown, M. A. H. Smith, V. Malathy Devi, D. Chris
Benner, and M. Dulick, Air-Broadening of **H~2~O** as a function of
Temperature: 696 -- 2163 cm^-1^. (submitted to J. Mol. Spectrosc.).

14\. A. Predoi-Cross, M. Brawley-Tremblay, L. R. Brown, V.M. Devi, and
D. C. Benner, Multispectrum analysis of air-broadening and
pressure-shifting coefficients of **^12^CH~4~** from 4100 to 4635
cm^-1^, submitted to J. Mol. Spectrosc.

***D. Chris Benner***, V Malathy Devi, Mary Ann H. Smith, Linda R.
Brown, Line shapes in the q branch of the
![](media/image1.png){width="0.10416666666666667in"
height="0.10416666666666667in"}~4~ band of methane, International
Symposium on Molecular Spectroscopy, Ohio State Univ., June, 2005.