The Coriolis Interaction between the v2 = 1 and v3 = 2 States of Nitrosyl Bromide: Anomalous Quadrupole Patterns and Interstate Transitions in the Millimeter-Wave Spectrum

The millimeter-wave rotational spectra of 79BrNO and 81BrNO in the v2 = 1 and v3 = 2 vibrational states have been reinvestigated. Measurements of the rotational spectrum in the region of maximum c-type Coriolis interaction between the two states allowed the previous analysis to be extended to account for some uncommon effects. For the most perturbed transitions the nuclear quadrupole hyperfine structure arises from coupling of not only the bromine nucleus, but also the nitrogen nucleus with the rotational angular momentum. These effects were satisfactorily fitted with a Hamiltonian describing Coriolis coupling in a molecule with two quadrupolar nuclei. The successful analysis of pure rotational transitions then allowed accurate prediction of rovibrational transitions, six of which were measured for 79BrNO and four for 81BrNO. Copyright 1998 Academic Press.     

Can Isotopic Substitution Change a Bright State into a Dark State? The Case of the v3 = 1 State of FClO3

High-resolution infrared spectra of monoisotopic samples of F35Cl18O3 and F37Cl18O3 have been recorded with the purpose of analyzing the nu3 fundamental at 535 cm-1. However, this band could not be observed whereas it had been seen and studied earlier in F35Cl16O3. To determine the parameters of the v3 = 1 state, indirect methods were used. Hot bands nun + nu3 - nu3 (n = 1 or 2) were first analyzed and their LSCD (Lower State Combination Differences) yielded rotational parameters of nu3. Then, with the help of nu1 + nu3, all rovibrational parameters of nu3 were obtained. Similar methods were applied to spectra of F35Cl16O3 and F37Cl16O3 to prove that the parameters of nu3 obtained in this fashion are identical to those determined directly for these isotopomers and are even more comprehensive. It is shown that the different character of nu3 in the two 18O and in the two 16O isotopomers is due to the fact that the former are much closer to a spherical top molecule ((A0 - B0)/A0 = 0.015). This is not only reflected in intensities different by two orders of magnitude but also in the very different values of alpha3B in these two pairs. Copyright 1997 Academic Press. Copyright 1997Academic Press     

Analysis of the nu8 + nu9 Band of HNO3, Line Positions and Intensities, and Resonances Involving the v6 = v7 = 1 Dark State

Using a high-resolution (R = 0.0025 cm-1) Fourier transform spectrum of nitric acid recorded at room temperature in the 1100-1240 cm-1 region, it has been possible to perform a more extended analysis of the nu8 + nu9 band of HNO3 centered at 1205.7075 cm-1. As in a recent analysis of this band [W. F. Wang, P. P. Ong, T. L. Tan, E. C. Looi, and H. H. Teo, J. Mol. Spectrosc. 183, 407-413 (1997)], the Hamiltonian used for the line positions calculation takes into account, for the upper state, the DeltaK = +/-2 anharmonic resonance linking the rotational levels of the v8 = v9 = 1 "bright" vibrational state and those of the "dark" v6 = v7 = 1 vibrational state. More than 4800 lines were assigned in the nu8 + nu9 band, which involve significantly higher rotational quantum numbers than in previous works. On the other hand, and surprisingly as compared to previous studies, the nu8 + nu9 band appears to be a hybrid band. In fact, nonnegligible B-type transitions could be clearly identified among the much stronger A-type lines. Accordingly, a set of individual line intensities were measured for lines of both types and were introduced in a least-squares fit to get the A- and B-type components of the transition moment operator. Finally, a synthetic spectrum of the 8.3-μm region of HNO3 has been generated, using for the line positions and line intensities the Hamiltonian constants and the expansion of the transition moment operator which were determined in this work. In this way, the B-type and the A-type components of the nu8 + nu9 band appear to contribute for about (1/4) and (3/4), respectively, to the total band intensity. Copyright 1999 Academic Press.     

核磁共振T2谱M-P广义逆反演研究

基于广义逆和奇异值分解理论,研究核磁共振T2谱反演的截断法和阻尼法.首先给出反演问题的M-P广义逆解;然后对系数矩阵进行奇异值分解求其M-P广义逆,对奇异值进行截断或者加阻尼,保证解的稳定性兼顾其分辨率;最后利用迭代技术实现解的非负约束.数值仿真实验和岩心T2谱反演表明:对于双峰谱,在信噪比SNR≥10时,截断法和阻尼法反演T2谱的分辨率和稳定性都很高;截断法截断因子选择范围小,在SNR＜10时解的分辨率和稳定性差;阻尼法阻尼因子选择范围大,在SNR＜10时解的稳定性好,但短组分分辨率低,长组分分辨率高.对于三峰谱,当SNR≥20时,截断法和阻尼法反演的T2谱光滑连续,具有三峰结构;当SNR＜20时两者均不能反演出与构造谱接近的三峰谱.因此,2种方法可应用于SNR≥10的双峰谱和SNR≥20的三峰谱反演;从分辨率和稳定性、平滑噪声及截断和阻尼因子的选取上,阻尼法略优于截断法.     

Infrared Spectrum of Ozone in the 4600 and 5300 cm-1 Regions: High Order Accidental Resonances through the Analysis of nu1 + 2nu2 + 3nu3 - nu2, nu1 + 2nu2 + 3nu3, and 4nu1 + nu3 Bands

The very weak bands nu1 + 2nu2 + 3nu3 and 4nu1 + nu3 of 16O3 have been observed for the first time, using the Fourier transform spectrometer (FTS) of Reims and the usual experimental setup providing a large product p x l of approximately 38 Torr x 36 m. The upper levels of these A-type bands which are rather close in energy (they appear respectively at 5291.722 and 5307.790 cm-1) belong to two different sets of interacting polyads. To correctly reproduce the rotation-vibration energy levels and account for the observed perturbations, both bands are treated in a dyad approximation: the (123) state in the Coriolis resonance with the (330) state, and the (401) state in the Coriolis resonance with the (024) state. The assignments of the rotation-vibration levels of the (123) state are confirmed by measurements of line positions of the hot band nu1 + 2nu2 + 3nu3 - nu2 which has also been observed for the first time. The fits are very satisfactory: the r.m.s. deviation for 249 energy levels of the (123) state is 2.4 x 10(-3) cm-1 and is 2.0 x 10(-3) cm-1 for 266 levels of the (401) state. These r.m.s. are near experimental accuracy. Transition moments for the three observed bands are determined from measured line intensities. Copyright 1997 Academic Press. Copyright 1997Academic 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.