Rovibrational and Rotational Spectroscopy of Levels of Propyne around 1000 cm(-1).

Four vibrational levels in the energy region around 1000 cm(-1) were studied. These were the v(5)=1 and v(8)=1 fundamental levels, both components of the v(9)=v(10)=1 combination level (l(9)=l(10)=+/-1 and l(9)=-l(10)=+/-1), and both components of the v(10)=3 overtone level (l(10)=+/-1 and +/-3). New FTIR spectra with a synchrotron radiation source were recorded in the region of the "superhot" v(10)=3<--2 bands, which made possible the first assignment of levels of the v(10)=3(+/-1) sublevel. More than 330 new rotational transitions in the combination and overtone levels were measured by millimeter-wave spectroscopy betwen 50 and 360 GHz. The new data were analyzed simultaneously together with the previously assigned rovibrational data for the fundamental and combination levels and rotational data for the fundamental levels using a global model with all anharmonic, Coriolis, l-type, and alpha-resonances. Significant improvement of data reproduction and very good consistency with the Hamiltonian parameters of the lower vibrational levels v(9)=1 and v(10)=1, 2 were achieved. A strong dependence of the A(v) constant on the l(10) quantum number is found for propyne: this is shown to be characteristic of skeleton C-C identical withC or C-C identical withN bending modes in H(3)CCCH, H(3)CCN, and their fully deuterated species. Copyright 2001 Academic Press.

Rovibrational Spectroscopy of the v(5) = 1 Level of (28)SiDF(3).

The nu(5) fundamental band of trifluorosilane-d (SiDF(3)) at 627 cm(-1) was studied for the first time by high-resolution FTIR spectroscopy at a resolution of 2.4 x 10(-3) cm(-1). The analysis was performed simultaneously with available microwave and newly measured submillimeter-wave data in the approximation of an isolated degenerate fundamental level of a C(3 Kv) symmetric top molecule leading to a standard deviation of 0.22 x 10(-3) cm(-1) for the reproduction of the infrared wavenumbers, 36 kHz for the microwave, and 198 kHz for the submillimeter-wave frequencies, respectively. The unitary equivalence between the two reductions (Q and D) of the effective Hamiltonian applied in the analysis is demonstrated. Copyright 2000 Academic Press.

High-Resolution Spectrum and Rovibrational Analysis of the nu(2)/nu(5) Dyad of D(3)SiF near 700 cm(-1).

The nu(2) (A(1), 710.157 cm(-1)) and nu(5) (E, 701.717 cm(-1)) fundamental bands of D(3)(28)SiF have been studied by FTIR spectroscopy with a resolution of 2.4 x 10(-3) cm(-1). We assigned 1648 lines for the parallel band (J(max) = 50, K(max) = 21), 4279 for the perpendicular band (J(max) = 52, K(max) = 27), and in addition 671 perturbation-allowed transitions (J(max) = 50, K(max) = 12). The nearly degenerate v(2) = 1 and v(5) = 1 states are linked by (DeltaK = +/-1, Deltal = +/-1) and (DeltaK = +/-2, Deltal = -/+1) interactions, while the l(5) = +/-1 levels of nu(5) interact also by l(2, -1), l(2, 2), and l(2, -4) interactions. The first model with 36 free parameters, taking into account all these resonances through a nonlinear least-squares program, gave standard deviations of 1.56 x 10(-4) cm(-1) for 5997 nonzero-weighted IR data and 138 kHz for 8 MW data from the literature. The second model, in which the main Coriolis term was constrained to a force field value, used 37 parameters and gave similar standard deviations. A new determination of the A(0) and D(0)(K) ground state parameters was performed by two methods: either using differences between "forbidden" transitions differing by 3 in K or letting A(0) and D(0)(K) free in the global fit. The values obtained are fully compatible with those obtained previously by the "loop method." Copyright 2000 Academic Press.

Rovibrational Analysis of the nu(6) Bands of Four Symmetric Isotopomers of FClO(3).

High-resolution (ca. 5 x 10(-3) cm(-1)) infrared spectra of monoisotopic samples of F(35)Cl(16)O(3), F(37)Cl(16)O(3), F(35)Cl(18)O(3), and F(37)Cl(18)O(3) have been recorded in the region of the nu(6) fundamental band. This band is centered at 405.6055, 405.5097, 390.5406, and 390.4984 cm(-1), respectively. About 1000 nonzero-weighted transitions were fitted for each isotopomer with an isolated band model, obtaining a s.d. on the residuals close to the experimental precision. Three different reductions of the Hamiltonian have been tested and found almost equally good, although FClO(3) is a nearly spherical top molecule. Each includes the l(2, 2) interaction and either a d(t) DeltaK = +/-3 interaction term (reduction Q) an epsilon(t) DeltaK = +/-3 interaction term (reduction QD), or an l(2, -1) interaction (reduction D). Good agreement between the theoretical predictions for these reductions and the experimental data is observed. Copyright 1999 Academic Press.

High-Resolution FTIR and Millimeter-Wave Study of D(3)SiF: The Ground, v(3) = 1, and v(6) = 1 and 2 States.

The nu(6) (555.453 cm(-1)), the nu(3) (888.899 cm(-1)), and the very weak 2nu(6) infrared bands (2nu(-/+2)(6) 1101.734 cm(-1), 2nu(0)(6) 1100.102 cm(-1)) for the (28)Si species of D(3)SiF have been recorded with a resolution of 3.3, 2.4, and 5.0 x 10(-3) cm(-1), respectively. Millimeter-wave spectra up to 640 GHz of D(3)SiF in the ground, v(3) = 1, and v(6) = 1 and 2 states were measured. Ground state constants complete up to H constants including the K-dependent parameters A(0), D(0)(K), and H(0)(K) as obtained by the nu(+/-1)(6)/2nu(+/-2)(6)-nu(+/-1)(6)/2nu(-/+2)(6) loop method were determined by a merge of 2388 ground state combination differences with 59 rotational data. The v(3) = 1 and v(6) = 1 and 2 levels appear to be unperturbed intervibrationally for the J and K values that could be accessed. However, Deltal = Deltak = +/-2 and Deltal = +/-2, Deltak = -/+4 interactions affect the v(6) = 1 level while the v(6) = 2 levels undergo three interactions of Deltal = Deltak = +/-2, Deltal = +/-2, Deltak = -/+1 and Deltal = +/-4, Deltak = -/+2 type. Typically, for the different bands, 2000-4000 pieces of infrared data augmented by 36-120 rotational data were fitted together. Owing to the weakness of the 2nu(6) band, the body of v(6) = 2 data was enlarged by energies that are deduced from the 2nu(6)-nu(6) and nu(6) bands and which span in particular high K values. Comparison with available ab initio data derived from the harmonic and anharmonic force fields is made. Copyright 1999 Academic Press.

Simultaneous Rovibrational Analysis of the nu(2), nu(3), nu(5), and nu(6) Bands of H(3)(12)CF.

A total of 4892 transition wavenumbers of the nu(2), nu(3), nu(5), and nu(6) fundamental bands of H(3)(12)CF and 1469 frequencies of the rotational transitions in the v(2) = 1, v(3) = 1, v(5) = 1, and v(6) = 1 vibrational states have been fitted simultaneously by taking explicitly into account various Coriolis interactions, l-type interactions, and alpha-resonance terms between and within the vibrational states. The standard deviation of the fit using 71 parameters was 8.10 x 10(-5) cm(-1) for the infrared data and 0.198 MHz for the rotational data. This study clearly shows that in order to obtain a really quantitative fit of the highly precise data of vibration-rotational and rotational spectroscopy, it is necessary to fit all the data simultaneously using a variational approach. The deperturbed values of the upper state rotational constants differ significantly from those obtained previously in fitting the nu(3) and nu(6) bands as isolated bands and the nu(2)/nu(5) bands by a variational approach. This is important for the precise determination of the equilibrium structure of methyl fluoride (J. Demaison, J. Breidung, W. Thiel, and D. Papousek, Struct. Chem., in press). Besides this, the results can be used in further studies of the reduced Hamiltonians for more complicated systems of interacting vibrational levels. Copyright 1999 Academic Press.

The Interacting v6 = 2 Levels of D3Si35Cl: A Tool to Determine Ground State Constants from High-Resolution Spectra in the 440-590 and 900-1100 cm-1 Regions.

High-resolution FTIR spectra of monoisotopic D3Si35Cl have been recorded in the regions 440-590 cm-1 (nu3/nu6) and 900-1100 cm-1 (2nu6/nu3 + nu6/2nu3). A detailed rovibrational study was done for the 2nu06, 2nu-/+26, and 2nu3 overtone bands and for the 2nu+/-26-nu+/-16, 2nu06-nu-/+16, and (nu3 + nu+/-16)-nu+/-16 hot bands. For the first time the interactions occurring between the v6 = 2, v3 = v6 = 1, and v3 = 2 levels of any trideuterated silyl halide have been analyzed. The (nu3 + nu+/-16)-nu+/-16 hot band served to obtain accurate energies of the v3 = v6 = 1 level, the nu3 + nu6 combination band not being detectable on our spectra. The first experimental determination of A0 and D0K for this molecule was undertaken by a well-established method, using the nu6, 2nu+/-26-nu+/-16, and 2nu-/+26 bands. Ground state energy differences DeltaK(J) = E0(J, K) - E0(J, K - 3) were calculated for K values from 2 to 16. By a least-squares fit of 163 such differences, the A0 and D0K values thus obtained were (in cm-1): A0 = 1.4278230(8) and D0K = 5.3916(31) x 10(-6). Copyright 1999 Academic Press.

High-Resolution Study of the First Stretching Overtones of H3Si79Br.

The Fourier transform infrared spectrum of monoisotopic H3Si79Br (resolution 7.7 x 10(-3) cm-1) was studied from 4200 to 4520 cm-1, in the region of the first overtones of the Si-H stretching vibration. The investigation of the spectrum revealed the presence of two band systems, the first consisting of one parallel (nu0 = 4340.2002 cm-1) and one perpendicular (nu0 = 4342.1432 cm-1) strong component, and the second of one parallel (nu0 = 4405.789 cm-1) and one perpendicular (nu0 = 4416.233 cm-1) weak component. The rovibrational analysis shows strong local perturbations for both strong and weak systems. Seven hundred eighty-one nonzero-weighted transitions belonging to the strong system [the (200) manifold in the local mode picture] were fitted to a simple model involving a perpendicular component interacting by a weak Coriolis resonance with a parallel component. The most severely perturbed transitions (whose ||obs-calc || values exceeded 3 x 10(-3) cm-1) were given zero weights. The standard deviations of the fit were 1.0 x 10(-3) and 0.69 x 10(-3) cm-1 for the parallel and the perpendicular components, respectively. The weak band system, severely perturbed by many "dark" perturbers, was fitted to a model involving one parallel and one perpendicular band, connected by a Coriolis-type resonance. The K" . DeltaK = +10 to +18 subbands of the perpendicular component, which showed very high observed - calculated values ( approximately 0.5 cm-1), were excluded from this calculation. The standard deviations of the fit were 11 x 10(-3) and 13 x 10(-3) cm-1 for the parallel and the perpendicular components, respectively. Copyright 1998 Academic Press.

Simultaneous Rovibrational Analysis of the nu2, nu3, nu5, and nu6 Bands of H313CF.

A total of 6071 transition wavenumbers of the nu2, nu3, nu5, and nu6 fundamental bands of H313CF and 1689 frequencies of the rotational transitions in the v2 = 1, v3 = 1, v5 = 1, and v6 = 1 vibrational states have been fitted simultaneously by taking into account various Coriolis interactions, l-type interactions, and alpha-resonance terms between and within the vibrational states. The standard deviation of the fit using 75 parameters was final sigma = 7.63 x 10(-5) cm-1 for the infrared data and 0.150 MHz for the rotational data. The possibility of obtaining a quantitative fit of the very precise data of high-resolution Fourier transform and submillimeter-wave spectroscopy for a semirigid symmetric top molecule is discussed. Copyright 1998 Academic Press.

High-Resolution FTIR Study of the (nu3 + nu4, nu1 + nu4) Interacting System of Rovibrational Bands of PF3 Between 1100 and 1300 cm-1

With a resolution of 4.4 x 10(-3) cm-1, we were able to identify in this range the very weak nu2 + 2nu04 (A1) component near 1180 cm-1, the nu3 + nu4 band around 1205 cm-1 with its (A1 + A2) and E very intermixed components, and the nu1 + nu4 (E) band centered at 1238 cm-1. Three thousand six hundred transitions belonging to the (nu3 + nu4, nu1 + nu4) interacting system were fitted together with a model taking into account l(2, 2) interactions inside nu1 + nu4 and between (A1 + A2) and E components of nu3 + nu4, the l-vibrational resonance inside nu3 + nu4(A1 + A2), and the Coriolis interactions between nu1 + nu4 and nu3 + nu4(A1 + A2) on one hand and between nu1 + nu4 and nu3 + nu4 (E) on the other. Four available MW transitions were also included in the fit. A rms of 0.76 x 10(-3) cm-1 was obtained with 34 free parameters among 38. Normally the Fermi resonance, which links nu3 to nu2 + nu4 with a coupling term W234 = 2.86 cm-1, must connect each component of nu3 + nu4 with each component of nu2 + 2nu4. But since we have only little experimental information about the weak nu2 + 2nu04 component (120 assigned lines) and none about the dark nu2 + 2nu+/-24 component, it was not possible to introduce this resonance in the fit. However, the bandcenters' shifts were calculated since the basic coupling term W234 and the anharmonic constant x24 are well known. Therefore, according to this approximation, the very sensitive anharmonic constants x34 and g34 could be deduced. Of course the x14 Fermi-independent constant, derived directly from the (nu1 + nu4)0 bandcenter given by the fit, was certainly more accurate. Copyright 1998 Academic Press.

The First Si-H Stretching Overtone of H3SiD: Emergence of Local Mode Effects

The FTIR spectrum of H3SiD in the 4100-4500-cm-1 region was recorded at Doppler-limited resolution, and four bands were studied. At lower wavenumbers, two strong bands, which in the local mode picture can be assigned to (200, E) (nu0 = 4308.5667 cm-1) and (200, A1) (nu0 = 4307.8441 cm-1), were analyzed, and at higher wavenumbers, two weaker bands, namely (110, E) at 4378.1950 cm-1 and (110, A1) at 4375.9763 cm-1, were analyzed. A total number of approximately 1900 lines in the strong dyad and 1000 lines in the weak one were assigned and fitted with standard deviations of the residuals approximately 0.0008 cm-1. The strong system (200) is close to local mode behavior, with no x, y Coriolis term needed and only a small z Coriolis term, and simple arithmetic relations between vibration-rotation parameters are fulfilled as expected. The local mode behavior of the weak system (110) is less pronounced, but z and x, y Coriolis effects are smaller than in the Si-H stretching fundamentals. Comparison of computed and observed spectra provided a good estimate for the ratios of transition moments of the different bands: they are, in absolute value, proportional to 3.5:1.75:1:1 for (200, E), (200, A1), (110, E), and (110, A1), respectively. Copyright 1998 Academic Press.