JOURNAL OF MOLECULAR SPECTROSCOPY ARTICLE NO.

176, 329336 (1996)

0094

Fourier Transform Infrared Emission Spectroscopy of ND and PH

R. S. Ram and P. F. Bernath1
Department of Chemistry, University of Arizona, Tucson, Arizona 85721 Received November 17, 1995; in revised form January 17, 1996

The infrared vibration rotation bands of ND in the X 3S 0 state were recorded using a Fourier transform spectrometer. The bands were observed in a microwave discharge of a mixture of N2 and D2 in the presence of He. The rotational structure of six bands, 1 0, 2 1, 3 2, 4 3, 5 4, and 6 5, has been observed in the 1800 2600 cm 01 region. The analysis of these bands provides an independent determination of the ground state vibrational constants in addition to an improved set of rotational constants. The principal molecular constants for the ground state are
ve 2399.1255(299) cm01, vexe 42.1064(212) cm01, ae 0.254570(192) cm01, veye 0.1203(54) cm01

Be 8.908665(146) cm01,

re 1.036651(9) A.

The molecular constants for PH have also been refined by combining the previous infrared [J. Mol. Spectrosc. 122, 275281 (1987)] and the recent submillimeter-wave [Chem. Phys. Lett. 211, 443448 (1993)] measurements. 1996
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INTRODUCTION

NH is one of the most studied free radicals because of its importance in astrophysics (19), atmospheric sciences (10), and chemistry (1118). NH has been observed in the spectra of sun (1, 2), cool stars (36), interstellar medium (7), and comets (8, 9) and has tentatively been identified in the earths atmosphere (10). This radical is frequently observed in flames (1114) and is readily made by photodissociation or electron impact (1518). The laboratory spectra of NH date from 1893, when Eder (19) initially observed the A3P X3S0 transition near 3360 A. Since then there have been many investigations of this radical from the submillimeter to the vacuum ultraviolet regions of the spectrum. Most of the previous work on NH has been summarized in our previous papers (20, 21). There have been numerous recent theoretical calculations of the properties of NH including the dissociation energy (22), dipole moments (23), radiative properties, and the rates of predissociation (17, 18, 23 26). Most of the recent experiments on NH and ND have concentrated on the laser spectroscopy of highly excited Rydberg states (27 31). In spite of so much interest in NH, only limited spectroscopic data are available for the ND molecule. This molecule has previously been studied by Shimauchi (32, 33) and Kopp and co-workers (34, 35). These authors measured the 00,
Also Department of Chemistry, University of Waterloo, Waterloo, Ontario, Canada N2L 3G1.
1

11, and 22 bands of the A3P X3S0 transition at grating resolution, but the analysis of these bands does not provide the sufficient data to determine the equilibrium vibrational constants. Recently, Patel-Misra et al. (36) observed the spectrum of this molecule in the D /1 sequence of the A3P X3S0 transition using a molecular beam source. They measured the lines in the 10, 21, and 32 bands of this transition with a precision of {0.3 cm01. They combined these measurements with the previous data on the 00, 1 1, and 22 bands (3235) and reported the equilibrium vibrational and rotational constants for ND. These constants have relatively large uncertainty because of limited resolution. The high-resolution vibrationrotation spectra of the ground state of NH have been measured by Boudjaadar et al. (37) and Chackerian et al. (38), and the far-infrared laser magnetic resonance spectra of the a1D state of NH and ND have been studied by Leopold et al. (39). In the most recent work on ND, Saito and Goto (40) have observed the submillimeter-wave spectrum and reported precise rotational constants including the hyperfine parameters for the 0 vibrational level of the X3S0 state. In the present work, we report the observation of six vibration rotation bands of ND at 0.01 cm01 resolution using a Fourier transform spectrometer. From the analysis of these bands, we have characterized the first seven vibrational levels of the ground X3S0 state. The present results provide a significant improvement in the molecular constants of ND.

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RAM AND BERNATH

(41), then the calibration was transferred to the spectrum of ND. The spectra were measured using a program called PCDECOMP developed at Kitt Peak. The measurements of the strong and unblended lines, which are observed with a maximum signal-to-noise ratio of 15:1 are expected to be accurate to {0.001 cm01. In the 22402390 cm01 spectral region the lines of ND are overlapped with strong atmospheric CO2 absorption. The lines located under the absorption lines of CO2 could not be measured. The lines of ND falling at the edge of the CO2 absorption features are not as accurate as the unblended lines and were therefore given lower weights in the final fit.
RESULTS AND DISCUSSION

(a) Analysis of ND VibrationRotation Bands The structure of each band consists of three R and three P branches. The low N lines of the R and P branches could be easily identified by their characteristic triplet pattern. For a particular value of N, the three spin components of the 3 0 S state have J values J N / 1, N, and N 0 1 for the F1, F2, and F3 spin components, respectively. This triplet pattern is clearly illustrated in Fig. 1, in which the three components of several R(N ) and P(N ) lines have been marked with the corresponding J quantum numbers. The splitting in the lines decreases rapidly with increasing J, and the components become unresolved at a J value ranging from 8 to 15 in the different bands. The R branches of each of these bands form a head at relatively high N values. For example, in the 10 band the R head is formed at R(N 26). After the head, the returning lines again show signs of

FIG. 1. A part of the spectrum of ND showing some R(N ) and P(N ) lines in different vibration-rotation bands. The J quantum numbers associated with each transition have also been provided.

EXPERIMENTAL

The vibrationrotation bands of ND were produced in an electrodeless microwave discharge through a flowing mixture of 0.13 Torr of N2, 0.13 Torr of D2, and 0.8 Torr of He. The discharge tube was made of quartz and had a diameter of about 12 mm. The emission from the lamp was focussed on the entrance aperture of the 1-m Fourier transform spectrometer associated with the McMathPierce telescope of the National Solar Observatory. The spectrometer was equipped with a KCl beam splitter and liquid-nitrogen-cooled InSb detectors. The use of a Ge filter limited the observation of the spectra to the 18005000 cm01 spectral region. A total of 20 scans were coadded in about 1 hr at a resolution of 0.01 cm01. In addition to ND bands, this spectrum also contained molecular lines of the w1P a1D transition of N2 and many atomic lines of the He, N, and D atoms. Because of a lack of strong CO lines in this spectrum, we decided to use some strong atomic lines as transfer standards for wavenumber calibration. For this purpose, we chose a separately recorded spectrum in which both CO and the atomic lines were strong. The atomic lines were first calibrated using the CO lines

FIG. 2. A part of the R branch of the 43 band near the head.

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TABLE 1 Line Positions (in cm01) in the VibrationRotation Bands of ND

Note. The observed minus calculated wavenumbers are in 104 cm01.

TABLE 1 Continued

INFRARED EMISSION SPECTRA OF ND

333

TABLE 1 Continued

spin-splitting but only a small number of returning lines could be picked-out because of their very weak intensity. A part of the 43 band showing the formation of the R head is presented in Fig. 2. The observed rotational lines are reported in Table 1, labeled with their J values (not N ). In the fundamental 10 band, lines have been observed up to R(N 34) and P(N 13). The P-branch lines are weak in intensity because of strong HermanWallis effects (38). In fact, no P-branch lines were identified for the 65 band and only a few low-N P lines were identified in the 54 and 43 bands (Table 1). The observed rotational lines of the individual bands were initially fitted separately using the customary 3S0 Hamiltonian. An explicit listing of the matrix elements for the 3S0 Hamiltonian is provided in our previous paper on NH (20). The initial constants obtained for the 0 vibrational level were found to be in reasonable agreement with the constants of Saito and Goto (40) obtained from the submillimeter-wave spectrum. The final set of constants were obtained by fitting the data of all of the bands simultaneously to provide a single set of constants (Table 2). In this fit the hyperfine-free submillimeter pure rotational wavenumbers for the N 1 r 0 transition of Saito

and Goto (40) were also included. The values used were 491 943.2365, 522 069.9217, and 546 150.3924 MHz for J 0 1, 2 1, and 1 1 transitions, respectively. For the 2, 3, 4, 5, and 6 vibrational levels, the constants L and gHv were not determined and were fixed to zero. The constants of Table 2 were used to determine the equilibrium molecular constants for the ground state, which are provided in Table 3. The ve value that we determine is in reasonable agreement with the value obtained by PatelMisra et al. (36) but vexe differs by 1.25 cm01. Their ground state DG(1/2) and DG(3/2) values of 2317.52(20) and 2235.77(30) cm01 (36) are also considerably different than the present values of 2315.23753(23) and 2231.73836(43) cm01, respectively. Patel-Misra et al.s B values, however, agree well with the present constants, within experimental error. Not surprisingly, since we used their data, our 0 rotational constants are also in excellent agreement with the constants of Saito and Goto (40). The equilibrium constants of ND result in the ground state equilibrium bond length of 1.036651(9) A which can be compared with the bond length re 1.03675 A for the ground state of NH (20). The recommended dissociation energy D0 is 77.7 kcal/mole (27 200 cm01) for NH (22).

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RAM AND BERNATH

TABLE 2 Rotational Constants (in cm01) for the X3S0 State of ND

Our data for vibration rotation levels up to 6, N 21 enable about 55% of the potential well of ND to be mapped. (b) Redetermination of Molecular Constants of PH We had some initial difficulty in combining the ND measurements with the pure rotational transitions of Saito and

TABLE 3 Equilibrium Constants (in cm01) for the X3S0 State of ND

Goto (40). As we were checking our computer program it was noticed that the constants reported in our previous work on PH (42) do not reproduce the high J lines within the experimental error. In addition, submillimeter-wave measurements have also been reported recently for PH (43). We therefore decided to refit our previous vibrationrotation measurements along with the pure rotation lines in order to obtain improved constants for the ground state of PH. The new set of molecular constants for the ground state of PH are provided in Table 4 and the equilibrium constants in Table 5.
CONCLUSION

The infrared emission spectra of six vibrationrotation bands of ND have been observed at high resolution using a Fourier transform spectrometer. The analysis of these bands provides a set of rotational constants for the 0, 1, 2, 3, 4, 5, and 6 vibrational levels of the X3S0 state. A much improved set of equilibrium vibrational and rotational constants was determined. Improved molecular constants for PH

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1996 by Academic Press, Inc.

INFRARED EMISSION SPECTRA OF ND

335

TABLE 4 Rotational Constants (in cm01) for the X3S0 State of PH

operated by the Association of Universities for Research in Astronomy, Inc., under contract with the National Science Foundation. The research described here was supported by funding from the NASA laboratory astrophysics program. Some support was also provided by the Natural Sciences and Engineering Research Council of Canada. We also thank S. Saito for providing the hyperfine-free submillimeter frequencies for ND at our request.

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TABLE 5 Equilibrium Constants (in cm01) for the X3S0 State of PH

have also been provided by combining our previous infrared measurements (42) with the submillimeter-wave measurements of Goto and Saito (43).
ACKNOWLEDGMENTS
We thank J. Wagner and C. Plymate of the National Solar Observatory for assistance in obtaining the spectra. The National Solar Observatory is

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