The Spectrum of Hot Water: Rotational Transitions and Difference Bands in the (020), (100), and (001) Vibrational States

Analysis of the hot H2 16O spectrum, presented by Polyansky et al. (1996, J. Mol. Spectrosc. 176, 305-315), is extended to higher vibrational states. Three hundred thirty mainly strong lines are assigned to pure rotational transitions in the (100), (001), and (020) vibrational states. These lines, which involve significantly higher rotational energy levels than were known previously, are assigned using high-accuracy variational calculations. Transitions in (020) are assigned up to Ka = 18, compared with the maximum Ka of 10 known previously. Crossings of vibration-rotation energy levels result in the observation of extra intensity-stealing transitions. In particular, this leads to the assignment of (020)-(100) and (100)-(020) rotational difference band transitions in addition to the conventional pure rotational lines in (020) and (100) states. These extra lines increase the number of transitions and they are likely to complicate the pure rotational water spectrum in higher excited vibrational states to an even greater extent. A few lines from our previous work on the pure rotational spectrum of hot water in the (000) and (010) vibrational states are also reassigned and some further assignments are made. Copyright 1997 Academic Press. Copyright 1997Academic Press

On the Spectroscopically Determined Potential Energy Surfaces for the Electronic Ground States of NO2 and H2O

Previous spectroscopically determined potentials for both H216O and NO2 are discussed. It is shown that a recent H216O potential energy surface due to D. Xie and G. Yan (1996. Chem. Phys. Lett. 248, 409), which was determined by fits to vibrational term values alone and was claimed to be more accurate than other published spectroscopically determined potentials for this system, actually gives unacceptably poor results for rotationally excited water. Reasons for this failure are discussed and the dangers of relying on vibrational term values alone are emphasized. Previous spectroscopic potentials for ground state NO2 are all found to have problems with unphysical minima ("holes"). Starting from the potential energy surface for the ground (&Xtilde;2A1) electronic state of NO2 constructed by S. A. Tashkun and P. Jensen (1994. J. Mol. Spectrosc. 165, 173) using the approximate MORBID approach a suitable starting point for fits using an exact kinetic energy operator approach was constructed. Least-squares fits to 17 potential parameters gives a potential which reproduces 173 vibrational term values with a standard deviation of only 2.8 cm-1 in the low-energy region (<10 000 cm-1). For many even levels below, and all levels above, approximately 10 000 cm-1 the first excited electronic state (Ã2B2) perturbs the vibrational energy levels of the ground state. We were unable to fit these levels. Tests show that the resulting effective potential surface has no problems with unphysical holes and gives a reasonable representation of the rotational structure of the low-lying vibrational states of NO2. Copyright 1997 Academic Press. Copyright 1997Academic Press

Water Vapor Line Assignments in the Near Infrared.

The high-resolution spectrum of water vapor between 13 200 and 16 500 cm-1 recorded by J.-Y. Mandin, J-P. Chevillard, C. Camy-Peyret, J.-M. Flaud, and J. W. Brault (1986. J. Molec. Spectrosc., 116, 167) is analyzed using high-accuracy linelists obtained using ab initio calculations and spectroscopically determined potential. Assignments to H216O transitions are presented for 663 of the 795 unassigned lines presented in the original paper. In addition, 38 lines are reassigned. The majority of these assignments and reassignments are confirmed by combination differences. These assignments significantly extend the measured data for the 4nu and 4nu + delta polyads and provide the first information on the (240), (033), (160), (170), and (071) bands. It is likely that a significant fraction of the remaining unassigned lines belong to H218O. Copyright 1998 Academic Press.

High-Temperature Rotational Transitions of Water in Sunspot and Laboratory Spectra

Assignments are presented for spectra of hot water obtained in absorption in sunspots (T approximately 3000°C and 750

Hot Bands of Water up to 6nu2-5nu2 in the 933-2500 cm-1 Region.

Emission spectra have been recorded for hot water at temperatures up to 1550 degreesC. Separate spectra have been recorded in the 800-1900 and 1800-2500 cm-1 range. Assignments are made using a linelist generated from high accuracy, variational nuclear motion calculations, and energy differences. The spectra contain many hot bending transitions of the form (0n0)-(0n-10), where states up to n = 6 have been assigned. Detailed analysis shows that the spectra contain lines from 34 separate vibrational bands including other hot bending transitions and the difference bands (030)-(100), (110)-(020), (011)-(020), (100)-(010), (040)-(110), (040)-(011), (120)-(030), (012)-(030), (011)-(100), (110)-(001), and (101)-(110), all of which have not been observed previously. From a total of 8959 lines recorded, 6810 have been assigned; 4556 of these lines are new. These spectra represent the first detection of the (060) vibrational band, for which a band origin of 8870.54 +/- 0.05 cm-1 is determined. The (050) band origin is confirmed as 7542.40 +/- 0.03 cm-1. The assignments extend the range of J and Ka values observed for the bending states, particularly for (050) and (060), where 63 and 27 different rotational levels, respectively, have now been observed; 53 frequencies given in HITRAN are corrected. Copyright 1999 Academic Press.

Cavity-Ring-Down Spectroscopy on Water Vapor in the Range 555-604 nm.

The method of pulsed cavity-ring-down spectroscopy was employed to record the water vapor absorption spectrum in the wavelength range 555-604 nm. The spectrum consists of 1830 lines, calibrated against the iodine standard with an accuracy of 0.01 cm(-1); 800 of these lines are not obtained in the HITRAN 96 database, while 243 are not included in the newly recorded Fourier transform spectrum of the Reims group. Of the set of hitherto unobserved lines, 111 could be given an assignment in terms of rovibrational quantum numbers from a comparison with first principles calculations. Copyright 2001 Academic Press.