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JOURNAL OF MOLECULAR SPECTROSCOPY ARTICLE NO.

190, 341–352 (1998)

MS987582

Fourier Transform Emission Spectroscopy of the A2 –X2 Transition of SiH and SiD
R. S. Ram, R. Engleman Jr.,1 and P. F. Bernath2
Department of Chemistry, University of Arizona, Tucson, Arizona 85721 Received January 13, 1998; in revised form March 26, 1998

The emission spectra of the A2 –X2 transition of SiH and SiD have been observed at high resolution using a Fourier transform spectrometer. The molecules were excited in a Si hollow cathode lamp by passing a discharge through a mixture of Ne and a trace of H2 or D2. The present data, combined with the previous infrared vibration–rotation measurements, have been used to determine improved molecular constants for the ground and excited states of SiH and SiD. © 1998 Academic Press INTRODUCTION

SiH is a free radical of fundamental importance. In recent years, there have been numerous experimental and theoretical studies of SiH because of its importance in astrophysics (1) and chemical vapor deposition of thin films (2– 4). Because of significant cosmic abundances of Si and H, there is a strong possibility that the SiH radical may be found in the interstellar medium and stellar atmospheres (5). SiH has already been identified in the spectra of sunspots (6 – 8). As a chemical intermediate this radical plays an important role in many industrial processes such as plasma vapor deposition, thin film formation, and semiconductor manufacturing. The primary diagnostic of silane plasmas has been the observation of the A2 –X2 transition of SiH by optical emission spectroscopy (9 –13), laser spectroscopy (14, 15), and laser optogalvanic spectroscopy (16). The emission spectrum of SiH has been known since 1930 when Jackson (17) observed a strong transition of SiH near 410 nm using an arc source. He obtained a rotational analysis of the 0 – 0 band and assigned it as the A2 –X2 transition. This analysis was later modified by Mulliken (18). The spectra of SiH and SiD were reinvestigated by Rochester (19), Douglas (20), and Klynning and Lindgren (21). Rochester (19) obtained an analysis of the 0 – 0 and 1–1 bands of SiH and the 0 – 0 band of SiD, whereas Douglas (20) observed the SiH bands at a higher dispersion and analyzed 0 – 0, 1– 0, 2–1, and 2–2 bands. In a more recent study Klynning and Lindgren (21) provided an analysis for 1–1 band of SiH and the 0 – 0, 1–1, 2–2, 1– 0, and 2–1 bands of SiD. Several higher-lying excited electronic states, B2 , C2 , D2 , and E2 , have also been observed for SiH and SiD (22–24). The B2 and D2 states were found
1 Present address: Department of Chemistry, University of New Mexico, Albuquerque, NM 87131. 2 Also at Department of Chemistry University of Waterloo, Waterloo, Ontario, Canada N2L 3G1.

to be strongly predissociated (22, 23). More recently, a new electronic state of SiH and SiD was detected near 46 700 cm 1 by resonance-enhanced multiphoton ionization spectroscopy (25). This state was tentatively assigned as a 2 state based on a computer simulation of the spectrum. Because of astrophysical interest in SiH, transitions in other spectral regions have also been investigated extensively. The lowest pure rotational transition lies outside of the spectral range available to radio astronomers, but lambda doubling transitions can be used to detect SiH. Similar radiofrequency transitions have been successfully used for the detection of OH and CH in the interstellar medium (26, 27). Wilson and Richards (28) obtained a -doubling frequency of 2940 300 MHz for J 0.5 by extrapolating the -doubling from high rotational levels populated in the optical experiment of Douglas and Elliott (5). Klynning et al. (29) remeasured their high dispersion plates in order to obtain the more precise values of the -doubling constants for the ground X2 state. From these measurements a value of 2968 6 MHz was predicted for the -doubling transition. Cooper and Richards (30) also carried out an ab initio calculation of this frequency. Freedman and Irwin (31) have refitted the line positions of the 0 – 0 and 1– 0 bands of Douglas (20) without first deriving term values [direct approach of Zare et al. (32)] and provided a value of 2932 MHz. The SiH vibration–rotation bands were observed by Knights et al. (33) in an emission study of a silane plasma in the 1800 –2300 cm 1 region. From this study the vibrational and rotational temperatures of 2000 and 485 K were obtained. The infrared spectra of SiH were also observed by Brown and Robinson (34), Brown et al. (35), Davies et al. (36), and Betrencourt et al. (37). Brown and Robinson (34) detected the fundamental 1– 0 band of SiH by laser magnetic resonance spectroscopy, while Betrencourt et al. (37) observed the 1– 0, 2–1, and 3–2 vibration–rotation bands at a resolution of 0.005

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There are several theoretical predictions of the spectroscopic properties of the SiH radical (47–54). A dipole moment of 0.118 D was predicted by Petterson and Langhoff (47), in excellent agreement with the calculated values of Lewerenz et al. (48) (0.124 D) and Meyer and Rosmus (49) (0.115 D). Park and Sun (50) have applied the valence shell Hamiltonian method base on quasi-degenerate manybody perturbation theory to calculate the molecular properties including the valence state energies. Theoretical calculations have also been focused on the study of geometrical structures, force constants, and vibrational spectra and heats of formation of silane (SiHn) and chlorinated silane molecules (SiHnClm) (51–55).
EXPERIMENTAL
R

FIG 1. A portion of the 0 – 0 band showing some low J lines in R11, R22, Q12, and sR21 branches of SiH.

cm 1 using a Fourier transform spectrometer and provided much improved constants for the ground state. In the most recent study of this radical, Seebass et al. (38) have measured several vibration–rotation lines in the 1– 0, 2–1, 3–2, 4 –3, and 5– 4 bands of five isotopomers of SiH and have determined a very precise set of ground state molecular constants including the spin-orbit constant of A0 142.8957 (8) cm 1. The intensity of the A2 –X2 electronic transition of SiH is of concern to astronomers and to material scientists. The absorption cross section and electronic transition moment of the A2 –X2 transition have been determined by Park (39) using a shock tube absorption technique, and a transition moment of 0.12 0.04 au has been obtained. The A2 –X2 transition of SiH has also been observed in vacuum UV photolysis experiments of silane (SiH4) and dichlorosilane (SiH2Cl2) by Washida et al. (40). In a recent paper Stamou et al. (41) have simulated the rotational intensity distribution of the 0–0 band of the A2 –X2 transition of SiH observed in emission from a radio frequency discharge and proposed a new set of molecular constants. There are several studies of the radiative lifetimes of the A2 state of SiH (7, 8, 42–45) using the solar spectrum (7, 8, 41), electron bombardment (43– 45), and laser-induced fluorescence (14, 46). The solar values, ranging from 569 to 3200 ns, have been estimated from the oscillator strengths f00 and are less reliable. The other experimental values range from 518 to 700 ns. A recent value of 534 23 ns has been obtained using the laser-induced fluorescence technique (46). There are several calculations providing the estimates of dissociation energy of SiH between 3.0 to 3.35 eV. An upper limit of 3.06 eV has been obtained from the analysis of predissociation in the 2 state (22), while a value of 3.34 eV was obtained from an analysis of the fluorescence lifetimes of the v 1 rotational levels of the A2 state (45). A summary of the experimental and theoretical heats of formation of SiH are tabulated by Jasinski et al. (2).

The SiH and SiD molecules were made in a demountable silicon hollow cathode lamp (56). The cathode was prepared by inserting a solid rod of boron-doped silicon into a hole in a copper block. The central part of the rod was then bored through to provide a uniform layer of silicon inside the cathode. The addition of 0.02% of boron to the silicon provided a material with good electrical conductivity. The lamp was operated at 470 V and 610 mA current with a slow flow of neon. Strong SiH bands were initially observed using neon carrier gas at 2 Torr without any added hydrogen. The hydrogen apparently came as impurity in the neon gas or in the vacuum system. The addition of more hydrogen did not increase the intensity of SiH bands. The SiD bands were observed by adding a trace of D2 gas to the neon flow. The spectra were recorded using the 1-m Fourier transform spectrometer associated with the McMath-Pierce Solar Telescope of the National Solar Observatory. The spectra in the 17 000 –35 000 cm 1 region were recorded using Si photodiode detectors and a CuSO4 filter. The SiH bands were recorded at 0.016 cm 1 resolution after coadding five scans in about 75 min of integration, while the SiD bands were recorded at 0.05 cm 1 after coadding 25 scans in 130 min of integration. The spectral line positions were extracted from the observed spectra using data reduction programs called PC-DECOMP and GREMLIN developed by J. Brault. The peak positions were determined by fitting a Voigt line shape function to each spectral feature. In addition to the SiH/SiD bands, the final spectra also contained Si and Ne atomic lines. The spectra were calibrated using the measurements of Ne atomic lines made by Palmer and Engleman (57). The SiH/SiD lines have widths of about 0.103 0.005 cm 1 and appear with a maximum signal-tonoise ratio of about 30:1 in the 0 – 0 band. Because of large widths and weak intensity, the high-J and weaker lines appear to be diffuse and slightly distorted. Part of the strange appearance of the lines could be due to the presence of unresolved

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THE A2 –X2

SYSTEM OF SiH AND SiD

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TABLE 1 Vacuum Wavenumbers (in cm 1) of the A2 –X2II System of SiH

isotope structure for high-J lines. The absolute accuracy and precision of the measurements of sharp and unblended lines is expected to be of the order of 0.003 cm 1. However, the uncertainty of the weaker and blended lines could be as high as 0.005 cm 1.

RESULTS AND DISCUSSION

The SiH and SiD bands are located in the 21 000 –25 000 cm 1 region that covers the v 0 and v 1 sequences. The bands in the v 1 sequences are very weak and could

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TABLE 1—Continued

not be measured. In the v 0 sequence the 0 – 0 band is the strongest and the 1–1 band is about 20% of the intensity of the 0 – 0 band. In this analysis we have only included the lines of these two bands. The 2–2 band is very weakly present in our

spectra and a few Q-branch lines were seen near the heads, but the data were not sufficient for a meaningful analysis. In a 2 –2 transition there are six strong main branches, P1, P2, Q1, Q2, R1, and R2, each of which is doubled by lambda

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SYSTEM OF SiH AND SiD

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TABLE 1—Continued

doubling in the 2 state. These are the only branches that are allowed if both states obey pure Hund’s case (a) coupling or if both states have pure Hund’s case (b) coupling. For SiH, however, the A2 state changes from approximately Hund’s case (a) to Hund’s case (b) as J increases and several satellite branches become allowed. In total six additional satellite branches (QR12, PQ12, OP12, SR21, RQ21, and QP21) are expected in each band. In the 0 – 0 band all of these branches have been identified. In the 1–1 band some of the satellite branches, such as OP12 and QP21, could not be identified because of their very weak intensity. In SiD some of the satellite branches also were not observed in the 0 – 0 and 1–1 bands. Although Klynning and Lindgren (21) observed more bands in their study, the Fourier transform measurements are expected to be more precise by about an order of magnitude. A part of the 0 – 0 band of SiH showing some low J lines of a few branches has been provided in Fig. 1. As shown, the -doubling is resolved even for the lowest J lines observed. The observed line positions of SiH and SiD bands have been provided in Tables 1 and 2. In order to determine the rotational constants, the observed line positions of different bands were fitted with the effective N2 Hamiltonian of Brown et al. (58). The 2 matrix element of this Hamiltonian is provided by Amiot et al. (59), and those for a 2 state are provided by Brown et al. (60). The lines in each of the vibrational bands were initially fitted separately using a nonlinear least-squares procedure. In the final fit the zero field wavenumbers of the 1–0 and 2–1 vibration–rotation bands calculated by Brown (61) (provided for convenience in Table 3), the infrared vibration– rotation bands of Betrencourt et al. (37), and far infrared frequencies calculated from the constants of Brown et al. (35) provided in the Table 2 of Betrencourt et al. (37) were combined with our present measurements. These infrared and far infrared frequencies were weighted by the estimated uncertainties provided in the original papers. The weights for the weaker and blended lines

were chosen according to the signal-to-noise ratio and extent of blending. The constants for SiH and SiD obtained in this fit are provided in Tables 4 and 5. The final reduced standard deviations are 1.20 for SiH and 1.14 for SiD. For convenience, the ground and excited state term values for SiH and SiD are also provided in Tables 6 and 7, respectively. The spectroscopic parameters Tv (except v 0), Av, v, Dv (except v 0), Bv, Dv, Hv, qv, qDv, pv, and pDv were determined in the ground state. The term value for the v 0 vibrational level of the ground state (T0) was held fixed to zero. Except for qv, qDv, pv, and pDv, all the above parameters were determined in the excited A2 state. The inclusion of high-J vibration–rotation lines from Betrencourt et al. (37) is expected to improve the determination of distortion constants in the ground state and hence help break the strong correlations with the excited state. The present ground state values are in excellent agreement with the previously reported values (35–38), partly because of the inclusion of all the previous infrared measurements. In particular the present values of G (1/2) 1971.03904(35) cm 1, A 0 1 142.88778(39) cm can be compared by the recent values of G (1/2) 1971.0413 cm 1, A 0 142.8952 cm 1 obtained by Seebass et al. (38) in their laser magnetic resonance experiment. The values of G (1/2) 1970.78 cm 1, A 0 142.83 cm 1 were obtained by Klynning and Lindgren (21). Some of the discrepancies are caused by our adoption of the N2 Hamiltonian rather than the energy level expressions used by Klynning and Lindgren (21). It has been shown by Brown and Watson (62) that the ADv and v parameters cannot be determined simultaneously for a 2 state. In their analysis Klynning and Lindgren (21) determined ADv (AJ in their notation) instead of v. The separation of these two parameters is possible only by isotopic substitution, and Betrencourt et al. (37) decided to determine v rather than ADv. In the most recent infrared study of this radical, Seebass et al. (38) observed the spectra of five isotopic species 28SiH, 29SiH, 30 SiH, 28SiD, and 29SiD and found an appreciable magnitude for

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TABLE 2 Vacuum Wavenumbers (in cm 1) of the A2 –X2II System of SiD

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SYSTEM OF SiH AND SiD

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TABLE 2—Continued

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TABLE 3 Hyperfine-Free Vibration-Rotation Lines (in cm

1

) of SiH and SiD (61)

the v parameter. Our results are consistent with the results of these two groups. Since the ground state molecular parameters are known with excellent precision from the previous infrared studies (35–38), the main purpose of the present study was to improve the molecular constants for the excited A2 state. It is therefore more interesting to compare the present excited state constants for the A2 state with the values obtained previously by Klynning and Lindgren (21) and Klynning et al. (29). Our G (1/2) 1662.36001(82) cm 1, A0 3.54137(82) cm 1 are significantly different from the values of G (1/2) 1660.58 cm 1, A0 3.62 cm 1 obtained by Klynning and Lindgren (21). The rotational constants for the v 0 vibrational level of the A2

state from their revised analysis of the 0 – 0 band [Klynning et al. (29)], however, compare better with our values. In this work they determined 0 instead of AD0 in the excited state while still keeping AD0 in the ground state. Their B0 7.28280(8) cm 1, D0 5.203(3) 104 cm 1, A0 3.544(2) and 0 0.0871 cm 1 compare well with our values of B0 7.287599(14) cm 1, D0 5.1881(13) 104 cm 1, A0 1 3.54137(82) and 0 0.089983(99) cm . The molecular constants of the v 0 and v 1 vibrational levels have been used to determine the equilibrium constants for SiH and SiD from an exact fit. The excited state equilibrium rotational constants obtained from this work are Be 7.502718(21) cm 1, e 0.215119(15) cm 1 for SiH and Be

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SYSTEM OF SiH AND SiD

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TABLE 4 Spectroscopic Constants (in cm 1) for the A2 –X2II System of SiH

3.878272(77) cm 1, e 0.076744(68) cm 1 for SiD. The values reported in parentheses are estimated uncertainties. Since these values have been determined from exact fits, the actual uncertainties in these values are expected to be much higher than the quoted values. The equilibrium bond lengths for the excited A2 state of SiH and SiD using these values are 1.5197816(21) Å and 1.521017(15) Å, respectively. In a previous study of this molecule, Verma (22) observed strong predissociation in the B2 and D2 states. From an analysis of these predissociations, Verma (22) estimated an upper limit of the dissociation energy of 3.06 eV for this

molecule. The lifetimes of a number of rotational levels of the v 0, 1, and 2 vibrational levels were measured by Carlson et al. (45) using the high-frequency deflection technique. They observed some decrease in the lifetimes of rotational levels at N 12 in v 1 F1 and F2 components. They found that the rotational levels up to N 11 of v 1 have average lifetimes of 594 10 ns, and for higher N this value decreases slowly to 470 ns in F1 (at N 18) and 405 ns in F2 (at N 16). They also found that the v 2 vibrational level has a very short lifetime of about 160 ns. From this observation, they concluded that the v 1 and 2 vibrational levels of SiH are affected by

TABLE 5 Spectroscopic Constants (in cm 1) for the A2 –X2II System of SiD

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Term Values (in cm

1

TABLE 6 ) for the Ground and Excited States of SiH

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Term Values (in cm

1

TABLE 7 ) for the Ground and Excited States of SiD

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RAM, ENGELMAN, AND BERNATH 23. G. Herzberg, A. Lagerqvist, and B. J. McKenzie, Can. J. Phys. 47, 1889 –1897 (1969). 24. P. Bollmark, L. Klynning, and P. Pages, Phys. Scr. 3, 219 –222 (1971). ` 25. R. D. Johnson III and J. W. Hudgens, J. Phys. Chem. 93, 6268 – 6270 (1989). 26. S. Weinreb, A. H. Barrett, M. L. Meeks, and J. C. Henry, Nature 200, 829 – 831 (1963). 27. O. E. H. Rydbeck, I. Ellder, and W. M. Irwine, Nature 246, 466 – 486 ´ (1973). 28. I. D. L. Wilson and W. G. Richards, Nature 258, 133–134 (1975). 29. L. Klynning, B. Lindgren, and U. Sassenberg, Phys. Scr. 20, 617– 619 (1979). 30. D. L. Cooper and W. G. Richards, J. Chem. Phys. 74, 96 –98 (1981). 31. R. S. Freedman and A. W. Irwin, Astron. Astrophys. 53, 447– 449 (1976). 32. R. N. Zare, A. L. Schmeltekopf, W. J. Harrop, and D. L. Albritton, J. Mol. Spectrosc. 46, 37– 66 (1973). 33. J. C. Knights, J. P. M. Schmitt, J. Perrin, and G. Guelachvili, J. Chem. Phys. 76, 3414 –3421 (1982). 34. J. M. Brown and D. Robinson, Mol. Phys. 51, 883– 886 (1984). 35. J. M. Brown, R. F. Curl, and K. M. Evenson, J. Chem. Phys. 81, 2884 –2890 (1984). 36. P. B. Davies, N. A. Isaacs, S. A. Johnson, and D. K. Russell, J. Chem. Phys. 83, 2060 –2063 (1985). 37. M. Betrencourt, D. Boudjaadar, P. Chollet, G. Guelachvili, and M. Morillon-Chapey, J. Chem. Phys. 84, 4121– 4126 (1986). 38. W. Seebass, J. Werner, W. Urban, E. R. Comben, and J. M. Brown, Mol. Phys. 62, 161–174 (1987). 39. C. Park, J. Quant. Spectrosc. Radiat. Transfer 21, 373–385 (1979). 40. N. Washida, Y. Matsumi, T. Hayashi, T. Ibuki, A. Hiraya, and K. Shobatake, J. Chem. Phys. 83, 2769 –2774 (1985). 41. S. Stamou, D. Mataras, and D. Rapakoulias, Chem. Phys. 218, 57– 69 (1997). 42. N. Grevesse and A. J. Sauval, J. Quant. Spectrosc. Radiat. Transfer 11, 65– 67 (1971). 43. W. H. Smith, J. Chem. Phys. 51, 520 –524 (1969). 44. W. H. Smith and H. S. Liszt, J. Quant. Spectrosc. Radiat. Transfer 11, 45–54 (1971). 45. T. A. Carlson, N. Duri, P. Erman, and M. Larsson, J. Phys. B 11, 3667–3675 (1978). 46. W. Bauer, K. H. Becker, R. Duren, C. Hubrich, and R. Meuser, Chem. ¨ Phys. Lett. 108, 560 –561 (1984). 47. L. G. M. Pettersson and S. R. Langhoff, Chem. Phys. Lett. 125, 429 – 432 (1986). 48. M. Lewerenz, P. J. Bruna, S. D. Peyerimhoff, and R. J. Buenker, Mol. Phys. 49, 1–24 (1983). 49. W. Meyer and P. Rosmus, J. Chem. Phys. 63, 2356 –2375 (1975). 50. J. K. Park and H. Sun, Chem. Phys. Lett. 195, 469 – 474 (1992). 51. A. F. Sax and J. Kalcher, J. Phys. Chem. 95, 1768 –1783 (1991). 52. L. A. Curtiss and J. A. Pople, Chem. Phys. Lett. 144, 38 – 42 (1988). 53. M. Larsson, J. Chem. Phys. 86, 5018 –5026 (1987). 54. P. Ho, M. E. Coltrin, J. S. Binkley, and C. F. Melius, J. Phys. Chem. 89, 4647– 4654 (1985). 55. J. Kalcher, Chem. Phys. 118, 273–284 (1987). 56. R. A. Keller, B. E. Warner, E. F. Zaleweski, P. Dyer, R. Engleman, Jr., and B. A. Palmer, J. Physique Colloq. 44, C7–C23 (1983). 57. B. A. Palmer and R. Engleman, Jr., ‘‘Atlas of Thorium Spectrum.’’ Report LA-9615, Los Alamos National Laboratory, Los Alamos, NM, 1983. 58. J. M. Brown, E. A. Colbourn, J. K. G. Watson, and F. D. Wayne, J. Mol. Spectrosc. 74, 294 –318 (1979). 59. C. Amiot, J.-P. Maillard, and J. Chauville, J. Mol. Spectrosc. 87, 196 –218 (1981). 60. J. M. Brown, A. S-C. Cheung, and A. J. Merer, J. Mol. Spectrosc. 124, 464 – 475 (1987). 61. J. M. Brown, private communication. 62. J. M. Brown and J. K. G. Watson, J. Mol. Spectrosc. 65, 65–74 (1977).

predissociation. We are unable to add much to these observations since our 1–1 band is weak in intensity and the 2–2 band is almost absent in our spectra.
CONCLUSION

The emission spectra of the A2 –X2 electronic transition of SiH and SiD have been measured with improved precision. The high-resolution measurements from spectra recorded with a Fourier transform spectrometer have been combined with the previous infrared vibration–rotation measurements (35–38) to extract improved molecular constants for the ground and excited states of SiH and SiD.
ACKNOWLEDGMENTS
We thank J. W. Brault and J. Wagner of the National Solar Observatory for assistance in obtaining the spectra. The National Solar Observatory is 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. Support was also provided by the Petroleum Research Fund administered by the American Chemical Society and the Natural Science and Engineering Research Council of Canada. We thank J. M. Brown for providing us the hyperfine-free vibration–rotation line positions for SiH and SiD.

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