Characterization of OCS-HCCCCH and N2O-HCCCCH dimers: Theory and experiment
A.J. Barclay, A. Pietropolli Charmet, K.H. Michaelian, N. Moazzen-Ahmadi
CCharacterization of OCS-HCCCCH and N O-HCCCCH dimers: Theory and experiment
A.J. Barclay, a A. Pietropolli Charmet, b K.H. Michaelian, c and N. Moazzen-Ahmadi a a Department of Physics and Astronomy, University of Calgary, 2500 University Drive North West, Calgary, Alberta T2N 1N4, Canada b Dipartimento di Scienze Molecolari e Nanosistemi, Università Ca' Foscari Venezia, Via Torino 155, I-30172, Mestre, Venezia, Italy c CanmetENERGY, Natural Resources Canada, One Oil Patch Drive, Devon, Alberta T9G 1A8, Canada
Address for correspondence: Prof. N. Moazzen-Ahmadi, Department of Physics and Astronomy, University of Calgary, 2500 University Drive North West, Calgary, Alberta T2N 1N4 Canada. bstract
The infrared spectra of the weakly-bound dimers OCS-HCCCCH, in the region of the fundamental band of OCS (2050 cm −1 ), and N O-HCCCCH, in the region of the ν fundamental band of N O (2200 cm −1 ), were observed in a pulsed supersonic slit jet expansion probed with tunable diode/QCL lasers. Both OCS-HCCCCH and N O-HCCCCH were found to have planar structure with side-by-side monomer units having nearly parallel axes. These bands have hybrid rotational structure which allows for estimates of the orientation of OCS and N O in the plane of their respective dimers. Analogous bands for OCS-DCCCCD and N O-DCCCCD were also observed and found to be consistent with the normal isotopologues. Various levels of ab initio calculations were performed to find stationary points on the potential energy surface, optimized structures and interaction energies. Four stable geometries were found for OCS-HCCCCH and three for N O-HCCCCH. The rotational parameters at CCSD(T*)-F12c level of theory give results in very good agreement with those obtained from the observed spectra. In both dimers, the experimental structure corresponds to the lowest energy isomer. ntroduction
Acetylene is a prototype molecule for examining weak intermolecular forces involving carbon-carbon triple bond. Pure and mixed acetylene clusters have been studied extensively both theoretically and experimentally [1, 2, 3, 4]. In particular, mixed dimers containing OCS and N O with acetylene are well characterized using microwave and infrared spectroscopy. To date, only one isomer of N O-HCCH has been observed in the gas phase [3, 5, 6]. This isomer, which is almost certainly the most stable structure, is planar with near parallel monomer units. For OCS-HCCH two isomers have been detected; a planar near-parallel structure analogous to the observed N O-HCCH and a T-shaped isomer having C symmetry, with OCS forming the stem of the T, and the S atom in the inner position pointing to the triple bond of C H [3, 7, 8]. The longer counterpart of acetylene, diacetylene, provides a simple system with multiple triple-bond sites; thus clusters containing diacetylene potentially display much richer-structured energy surfaces. For example, theoretical calculations in Ref. [9] identify three structural isomers, a Y-shaped -type hydrogen-bonded structure with C S symmetry, a parallel slipped structure with C symmetry, and a cross shaped structure with D symmetry. Since this dimer has not been observed experimentally, nor has its complete intermolecular potential surface been investigated with high-level ab initio calculations, it is unclear what type of tunneling dynamics exist in (HCCCCH) and if there are out of plane paths via the cross-shaped structure, or the situation is similar to acetylene dimer where the large amplitude tunneling takes place in the plane of the dimer. There are relatively few gas phase studies of mixed dimers containing diacetylene. The first of these is a microwave study of NH -HCCCCH and H O-HCCCCH by Matsumura et al. [10]. Here, NH -HCCCCH was found to be an axially symmetric complex where a diacetylene hydrogen bonds to the nitrogen in ammonia to form a symmetric top and H O-HCCCCH has a planar symmetry where a diacetylene hydrogen bonds to the oxygen of water. The structural similarities with NH -HCCH and H O-HCCH suggest that diacetylene closely parallels acetylene in complexes with other bases. On the other hand a dissimilar behavior might be expected when acetylene and diacetylene act as bases in complexes with acids. A study by Yang et al. [11] of HCN-HCCCCH in the infrared region found only a linear configuration despite the fact that both linear and T-shaped structures are observed in HCN-HCCH and the T-shaped isomer is strongly favored in the molecular beam expansion of HCN-HCCH. Although, this observation seems to confirm the dissimilar behavior between acetylene and diacetylene when they act as bases, Yang et al. [11] attributed the absence of the T-shaped isomer in their experiment to the very asymmetric top character of the HCN-HCCCCH which disperses its spectra and gives rise to an unfavorable partition function and consequently low signal to noise ratio. In the present paper, we observe and analyze the spectra of OCS-HCCCCH and OCS-DCCCCD, in the region of the fundamental of OCS, and N O-HCCCCH and N O-DCCCCD, in the region of the fundamental of N O. Both dimers were found to have planar C S symmetry with monomer axes nearly parallel to each other. Furthermore, the spectra have hybrid a-, b-type rotational structure which allow for good estimates of the orientation of OCS and N O in their dimers. The four independent structural constants obtained from the analysis of spectra for OCS-HCCCCH and OCS-DCCCCD are insufficient for accurate determination of an experimental structure. The same can be said in the case of N O-HCCCCH. Therefore, we carried out various levels of ab initio calculations in support of our experimental findings. Counterpoise-corrected binding energy calculations indicate that the observed structures are the most stable isomers. In addition, three less energetically favorable structures were found for OCS-HCCCCH and two for O-HCCCCH. Experimental rotational constants are in excellent agreement with the rotational constants at the CCSD(T*)-F12c level of theory. Our results closely parallel mixed acetylene complexes with OCS and N O. Computational details
To support our experimental analysis, as well as to characterize the stationary points on the potential energy surface (PES) of these complexes, we performed several ab initio calculations. As a first step, we searched the potential energy surface (PES) of both OCS-HCCCCH and N O-HCCCCH by means of density functional theory (DFT). Two different functionals, namely B3LYP [12, 13] and B2PLYP [14], were used employing the DFT-D3 dispersion corrections proposed by Grimme [15], in conjunction with the maug-cc-pVTZ basis set [16]. The inclusion of these corrections is mandatory since, even if DFT methods are nowadays widely employed for treating a wide variety of chemical problems, ranging from spectroscopic analysis to molecular complexes and adsorption processes (see for example Refs. [17, 18, 19, 20, 21, 22, 23, 24, 25), the role of dispersion contributions is fundamental for modeling correctly the energetics of van der Waals adducts [26, 27, 28]. The structures of the stationary points for both OCS-HCCCCH and N O-HCCCCH were first optimized at B3LYP-D3 level of theory and then refined using the B2PLYP-D3 functional. Calculations carried out with both functionals led to identification of four stationary points for OCS-HCCCCH and three for N O-HCCCCH; subsequent hessian calculations carried out on these optimized structures, corrected by the basis set superposition error (BSSE) using the counterpoise correction (CP) as proposed by Boys and Bernardi [29], confirmed that they correspond to true minima on the PES. These isomers are hown in Fig. 1 for OCS-HCCCCH and in Fig. 2 for N O-HCCCCH. We computed the corresponding counterpoise corrected (CP) values of both binding and interaction energies (hereafter labeled as BE and IE, respectively) at the B2PLYP-D3 level of theory for all of the structures. We corrected these BE values by also taking into account the zero-point vibrational (ZPV) correction for each species, defined as nn E (1) where the harmonic frequencies n (the index n labels the n -th vibrational mode) were obtained at B2PLYP-D3/maug-cc-pVTZ level. To determine a better estimate of the binding energy for all the structures, we performed additional single-point calculations on each of these optimized geometries at the coupled-cluster level of theory using the singles and doubles approximation augmented by a perturbative treatment of triple excitations, CCSD(T) [30, 31, 32], within the frozen core (fc) approximation. By using the correlation consistent basis sets cc-pVnZ basis set [33, 34, 35] both the Hartree-Fock self-consistent-field (HF-SCF) energies and the CCSD(T) correlation energies were extrapolated at the complete basis set (CBS) limit (at which the BSSE error vanishes), and then combined to correct for the error due to the basis-set truncation. CBS energies at HF-SCF level were evaluated using cc-pV n Z ( n = T, Q and 5) basis sets, and employing the e -Cn formula [36], while the CCSD(T) correlation contributions were computed using the n -3 expression [37] with the cc-pVTZ and cc-pVQZ basis sets. Subsequent corrections due to core-valence (CV) correlation effects were calculated as the difference between CCSD(T) energies (in conjunction with the cc-pCVTZ basis set [38]) obtained by correlating all electrons and within the fc approximation. Inclusion of the ZPV corrections yielded the best estimate values for the binding energies reported in the present work, which therefore were then used to identify the most stable isomer for both OCS-HCCCCH and N O-HCCCCH complexes. The esults for rotational constants, interaction and binding energies are summarized in Table 1. For the most stable isomer of both OCS-HCCCCH and N O-HCCCCH complexes, we carried out additional geometry optimizations at both CCSD(T) and CCSD(T*)-F12c [39] levels of theory and in conjunction with the cc-pVTZ and cc-pV n Z-F12 [40] basis sets ( n = D, T), respectively; for the latter, both the appropriate auxiliary basis sets [41] and its complement auxiliary basis sets (CABS) [42] were used. Finally, for these two structures, within the framework of the vibrational second-order perturbation theory (VPT2 [43, 44]) we computed the vibrational corrections vib i B to the corresponding equilibrium rotational constants ie B by means of the following expression vib i inn B (2) where the in are the vibration-rotation interaction constants ( i labels the inertial axis). These corrections were computed on the basis of the cubic force fields, which were calculated by using the maug-cc-pVTZ basis set and the B3PLYP functional (with the D3 corrections), in view of its good performance in modeling the anharmonic part of the potential [45], following the procedures established in previous works [46, 47]. We performed all DFT calculations employing the Gaussian suite of quantum chemical programs [48]; for both B3LYP and B2PLYP functionals, we employed the UltraFine grid available in Gaussian09 (corresponding to 99 radial and 590 angular points), because of its good results (see for example Refs. [18, 49]) for the calculations of anharmonic force field data. For the calculations carried out at coupled cluster levels of theory we used the MOLPRO program [50, 51] together with its appropriate software packages [52, 53, 54, 55, 56]. The optimized rotational parameters for the most stable isomers are given in Table 2. able 1. Theoretical molecular parameters for OCS-HCCCCH and N O-HCCCCH isomers optimized at DFT level of theory. a OCS-HCCCCH N O-HCCCCH Isomer I (S-in) Isomer II (O-in) Isomer III T-shaped Isomer IV Cross-shaped Isomer I (N-in) Isomer II (O-in) Isomer III Cross-shaped A a B a C a
886 803 670 1139 1092 1102 1394 BE (CP)b -776 -630 -584 -668 -727 -675 -612 BE (CP+ZPV)c -562 -313 -403 -352 -495 -285 -406 IE (CP)d -780 -633 -584 -668 -727 -679 -612 BE (CBS)e -682 -560 -504 -567 -700 -611 -570 BE (CBS+CV)f -694 -569 -513 -577 -705 -617 -577 BE (CBS+CV+ZPV)c -479 -252 -332 -384 -472 -227 -371 a Equilibrium rotational constants (in MHz) obtained from optimized geometries obtained with B2PLYP-D3 in conjunction with maug-cc-pVTZ basis set. Binding energies (BE) and interaction energies (IE) reported in cm -1 . b Counterpoise-corrected binding energy computed at B2PLYP-D3/maug-cc-pVTZ level of theory. c Binding energy including zero-point vibrational contribution evaluated at B2PLYP-D3/maug-cc-pVTZ level of theory. d Counterpoise-corrected interaction energy computed at B2PLYP-D3/maug-cc-pVTZ level of theory. e Binding energy obtained from extrapolated energies to the CBS limit at CCSD(T) level of theory (see text). g Binding energy obtained from extrapolated energies to the CBS limit at CCSD(T) level of theory corrected by CV-effects (see text). able 2. Equilibrium rotational constants (in MHz) obtained at different coupled cluster levels of theory for the OCS-HCCCCH and N O-HCCCCH isomers experimentally observed in the present work.
OCS-HCCCCH N O-HCCCCH Isomer I Isomer I CCSD(T) a CCSD(T*)-F12c b CCSD(T) a CCSD(T*)-F12c b A B C
847 885 1064 1097 a Optimized geometries obtained at CCSD(T, fc) level of theory in conjunction with cc-pVTZ basis set. b Optimized geometries obtained at CCSD(T*)-F12c level of theory in conjunction with VTZ-F12 basis set. Observed spectra
The spectra were recorded as described previously [57-59], using a pulsed supersonic slit jet apparatus, a diode laser for OCS-HCCCCH and a Daylight Solutions quantum cascade laser for N O-HCCCH. The expansion gas was a mixture of N O (0.1%) and C H or C D (0.3%) in helium as a carrier gas with a jet backing pressure of 8 atmospheres. The lower concentration of N O relative to HCCCCH was needed to minimize the formation of N O clusters, which are known to absorb in the 2220 cm -1 spectral region [3]. Similar conditions were used for OCS-HCCCCH and its deuterated isotopologue. Figure 1: The four isomers of OCS-HCCCCH using DFT level of theory. Isomer I, studied in this work, is the lowest energy structure. See Table 1 for energy ordering of the isomers.
Figure 2: The three isomers of N O-HCCCCH using DFT level of theory. Isomer I, studied in this work, is the lowest energy structure. See Table 1 for energy ordering of the isomers. he diacetylene was synthesized by the procedure described in Ref. [60]. DCCCCD was obtained by mixing HCCCCH with a 1 N solution of NaOD in D O as described by Etoh et al. [61]. The sample of diacetylene and diacetylene-d thus prepared were purified by repeated distillation under vacuum and then stored at LN temperature. The purity of the sample was checked using low resolution infrared spectroscopy. Spectral assignment and simulation were made using PGOPHER [62]. 2.1. OCS-HCCCCH results For all the minima of OCS-HCCCCH (listed in Table 1), the analysis of their structures (optimized at B2PLYP-D3/maug-cc-pVTZ level of theory) shows that there is an almost negligible variation in the intramolecular geometric parameters due to the complexation. Both the counterpoise corrected binding energies computed at DFT level of theory and those obtained from CCSD(T) extrapolated energies to the CBS limit identify isomer I (see Fig. 1) as the most stable form of OCS-HCCCCH (-2.22 kcal mol -1 at B2PLYP level of theory, -1.95 kcal mol -1 at CCSD(T) CBS limit). The inclusion of CV-effects is almost negligible, while the zero-point vibrational contributions reduce the binding energie (computed from extrapolated energies to the CBS limit at CCSD(T) level of theory) of isomer I to -1.37 kcal mol -1 . This isomer has a planar structure with nearly parallel side-by-side monomer units and the OCS S-atom on the inside (S-in). Furthermore, the calculated angle between the OCS monomer and the a inertial axis is 72 . Therefore the intramolecular fundamental in the region of the OCS monomer fundamental is an a/b-hybrid band, with a b-type transition moment which is larger than that for a-type transitions by a factor of ~3. Isomer II is also planar with a similar structure to isomer I, but with the OCS monomer unit in reverse orientation (O-in). Here, the calculated angle between the OCS monomer and the a inertial axis is 42 . This implies an a/b-hybrid band for the intramolecular undamental in the region of the OCS with almost equal transition moments for the a- and b-type transitions. The expected rotational structure for isomer III is a nearly pure a-type band, as the calculated angle between the OCS monomer and the a inertial axis in only 12 . Finally, isomer IV is non-planar and would give rise to a mostly c-type band. A segment of the experimental spectrum for OCS-HCCCCH, including the sharp Q-branch marked by an asterisk and a part of the R-branch, is shown in the second trace in Fig. 3. The corresponding segment for OCS-DCCCCD is illustrated in the bottom trace. With a 1:3 mixture of OCS and diacetylene we observe a relatively strong a/b-hybrid band, which could be simulated with a b-type transition moment about three times that of the a-type transition moment. This implies that the band observed is due to the most stable form. Further evidence for this assignment is given in section 3. A total of 245 transitions involving rotational levels up to J = 12 and a k were assigned for OCS-HCCCCH. Preliminary analysis of the spectrum confirmed that the upper state rotational levels with ' 6 a k are perturbed. The assigned transitions were then used to obtain 90 ground state combination differences (GSCD). These were used in a frequency analysis to obtain five ground state parameters. The upper state parameters were subsequently obtained from a frequency analysis of the assigned transitions with ' 6 a k while keeping the ground state parameters fixed. The frequency analysis for GSCD gave a weighted standard deviation of 0.00015 cm -1 and that for the upper vibrational state was 0.00018 cm -1 . The parameters thus obtained are listed in the second column of Table 3. The top two traces in Figure 3 show a comparison of observed and simulated spectra based on these parameters. Analysis of the band for OCS-DCCCCD was more straightforward, partly because the spectral region observed was more limited, to conserve the DCCCCD sample, and partly because he upper state rotational levels don’t seem to be affected by perturbations. A total of 159 transitions involving levels up to J = 12 and a k were assigned and analysed to obtain the parameters listed in column 3 of Table 3. The third and fourth traces in Fig. 3 show a comparison of simulated and observed spectra using these parameters. The assigned transitions are listed along with their corresponding residuals in Table A-1 for OCS-HCCCCH, including the perturbed transitions with ' 6 a k which were given zero weight, and Table A-2 for OCS-DCCCCD. Figure 3: Observed and simulated spectra of OCS-HCCCCH and OCS-DCCCCD. The simulation is based on the fitted parameters of Table 3, an effective rotational temperature of 2.5 K, and an assumed Gaussian line width of 0.0018 cm -1 . Blank regions in the observed spectra are obscured by absorptions due to OCS monomer . able 3. Molecular parameters for OCS – HCCCCH. a This work
CCSD(T*)-F12c OCS – HCCCCH
OCS – DCCCCD OCS – HCCCCH OCS – DCCCCD / cm -1 A' /
MHz 2891.907(68) 2692.82(28)
B' /
MHz 1242.930(34) 1205.53(12)
C' /
MHz 867.841(16) 831.664(79) D K ' / kHz c D JK ' / kHz c A" / MHz 2892.78(15) b e e B" / MHz 1244.416(74) b e e C" / MHz 869.008(55) b e e D K " / kHz b D JK " / kHz b Δ / a.m.u Å d d a Uncertainties (1 ) in parentheses are in units of the last quoted digit. b Ground state parameters were obtained from the lower state combination differences. These were held fixed during the frequency analysis of the upper state rotational levels. c Excited state quartic parameters were held fixed at their ground state values. d Inertial defect, c a b
I I I . e Equilibrium rotational constants at CCSD(T*)-F12c/VTZ-F12 level of theory augmented by vibrational corrections computed at B3LYP-D3 level (see text). O-HCCCCH results Figure 2 illustrates the three possible forms of N O-HCCCCH identified in the present work. For all the structures (obtained at B2PLYP-D3/maug-cc-pVTZ level of theory) the omplexation leads to negligible modifications in the intramolecular geometric parameters, as found for the isomers of OCS-HCCCCH. All the calculations carried out in the present work (see Table 1) identify isomer I (N-in) as the most stable form. Its binding energy, computed from extrapolated energies to the CBS limit at CCSD(T) level of theory corrected by CV-effects and taking into account zero-point vibrational contributions, is -1.35 kcal mol -1 . This isomer has a planar structure with two nearly parallel monomer units. Here, the calculated angle between the N O monomer and the a principal axis is 56 , implying that the intramolecular fundamental in the region of the N O monomer fundamental is an a/b-hybrid band with a b-type transition moment about 1.5 times that for the a-type transitions. The higher energy isomer (O-in) has a very similar structure with the N O monomer making an angle of 53 with the a axis, only 3 less than isomer I; thus the expected intramolecular bands for the two isomers have very similar rotational structure. Isomer III is non-planar with the N O monomer axis perpendicular to the ab plane, resulting in a purely c-type band. A segment of the experimental spectrum for N O-HCCCCH is shown in the second trace of Fig. 4. Unlike OCS-HCCCCH, the Q-branch, marked by an asterisk, shows much more structure. The corresponding segment for N O-DCCCCD is illustrated in the bottom trace. Again, we observe a relatively strong a/b-hybrid band which is simulated with the b-type transition moment ~1.5 times that of the a-type transition moment. Although the simulated spectrum with this ratio of the transition moments (1.5) gives better overall intensity agreement with the experimental spectrum than b-type/a-type = 1.3 as calculated for isomer II, this alone is insufficient to conclusively assign the observed band to isomer I. Further evidence in support of assignment of the observed band to isomer I is given in section 3. nalysis of the bands for N O-HCCCCH and N O-DCCCCD was straightforward. A total of 166 transitions involving levels up to J = 11 and a k for N O-HCCCCH and 121 transitions involving levels up to J = 10 and a k were assigned and analysed to obtain the parameters listed in columns 3 and 4 of Table 4. The weighted standard deviation of the fit for N O-HCCCCH was 0.00023 cm -1 and that for N O-DCCCCD was 0.00024 cm -1 . The first and third traces in Fig. 4 show the simulated spectra using these parameters. The assigned transitions along with their corresponding residuals are listed in Table A-3 for N O-HCCCCH and Table A-4 for N O-DCCCCD.
Figure 4: Observed and simulated spectra of N O-HCCCCH and N O-DCCCCD. The simulation is based on the fitted parameters of Table 4, an effective rotational temperature of 2.5 K, and an assumed Gaussian line width of 0.0022 cm -1 . Blank regions in the observed spectra are obscured by absorptions due to N O monomer . Table 4. Molecular parameters for N O – HCCCCH. a This work
CCSD(T*)-F12c N O – HCCCCH N O – DCCCCD N O – HCCCCH N O – DCCCCD / cm -1 A' /
MHz 4479.78(35) 4117.27(20)
B' /
MHz 1409.16(12) 1358.51(12)
C' /
MHz 1069.838(81) 1019.606(90) D K ' / kHz D JK ' / kHz -12.2(25) A" / MHz 4498.57(28) c c B" / MHz 1409.03(12) c c C" / MHz 1070.783(76) c c D K " / kHz Δ / a.m.u Å b b a Uncertainties (1 ) in parentheses are in units of the last quoted digit. b Inertial defect, c a b
I I I . c Equilibrium rotational constants at CCSD(T*)-F12c/VTZ-F12 level of theory augmented by vibrational corrections computed at B3LYP-D3 level (see text). Discussion and conclusions
Comparison of the theoretical rotational constants for OCS-HCCCCH at all levels of theory, columns 2-5 in Table 1 and columns 2-3 in Table 2, with the experimental rotational constants, column 2 in Table 3, clearly indicates that the observed dimer corresponds to the owest energy isomer identified in the present work. Moreover, the best agreement for both the dimers is obtained at the highest level of theory, CCSD(T*)-F12c/VTZ-F12. The results for the deuterated isotopologue, columns 3 and 4 in Table 3, provide further support for this assignment. This, together with the expectation that the jet conditions employed in this work favor the formation of the lowest energy structure, leaves very little doubt that isomer I in Fig. 1 corresponds to the species observed. Small and positive values for the inertial defects (Table 3) indicate that observed dimer is indeed planar. Positive contributions to the inertial defect result from Coriolis interactions associated with in-plane bending motions; in isomer I of OCS-HCCCCH these are larger than negative contributions from out-of-plane vibrations [63]. All of the arguments made above in support of isomer I of OCS-HCCCCH being the carrier of the observed band in the region of the fundamental of OCS can similarly be made for the most stable isomer of N O-HCCCCH. Therefore, the carrier of the intramolecular band in the region of the fundamental of N O is isomer I in Fig. 2. Again, the small and positive values for the inertial defects (Table 4) indicate that the observed dimer is planar. The slight increase in the magnitude of inertial defect, from 0.78 a.m.u. Å for OCS-HCCCCH to 0.96 a.m.u. Å , is consistent with the fact that N O-HCCCCH is a lighter dimer. The theoretical intermolecular distances for OCS-HCCCCH (S-in) and N O-HCCCCH (N-in) with the experimental vibrational shifts are listed in Table 5. In the case of OCS-HCCCCH, these are compared with the corresponding values for the two observed isomers of OCS-HCCH [3]. As can be seen, the intermolecular distance of R = 3.69 Å for OCS-HCCCCH (S-in) is comparable to that for the near-parallel isomer of OCS-HCCH (S-in, R = 3.61 Å) and expectedly much shorter than that for the T-shaped structure (R = 4.62). In the case of N O-CCCCH (N-in), the calculated intermolecular distance is for 3.43 Å, somewhat larger than R = 3.30 Å for N O-HCCH (O-in). The larger R for N O-HCCCCH (N-in) may be explained by the combination of the Van der Waals radii, 1.55 Å for the oxygen atom and 1.50 Å for nitrogen [64], and the fact that the center of mass is shifted by 0.07 Å from the central nitrogen atom toward the oxygen atom in the N O monomer unit. As always, the vibrational shifts are difficult to interpret. However, we note that the shifts for both diacetylene- and acetylene-containing species, as shown in Table 5, are consistently to lower frequency for dimers containing OCS and to higher frequency for dimers containing N O. Table 5. Comparison of intermolecular distance and vibrational shift between acetylene and diacetylene containing dimers
OCS-HCCCCH Near-parallel (S-in)
OCS-HCCH Near-parallel (S-in)
OCS-HCCH T-shaped a N O-HCCCCH Near-parallel (N-in) b N O-HCCH Near-parallel (O-in)
Intermolecular distance R (Å) 3.69
Vibrational Shift (cm -1 ) -6.085 -0.286 -5.688 +2.219 +5.346 a The calculated intermolecular distance for T-shaped OCS-HCCCCH is 4.52 Å. b For comparison the calculated intermolecular distance for N O-HCCCCH (O-in) is 3.60 Å.
In summary, we have observed and analyzed spectra of the most stable isomers of OCS-HCCCCH and N O-HCCCCH using the vibrational fundamentals of OCS and N O monomers in the 4 micron region as IR chromophores. Both dimers were found to have planar structure with nearly parallel monomer units. A combination of experimental evidence and theoretical calculations, at several different levels of theory, was used to identify the carriers of the infrared bands. Theoretical calculations predicted four isomers for OCS-HCCCCH and three for N O-HCCCCH, and the observed structures were assigned to the lowest energy structures on the potential energy surfaces. The observed spectra for OCS-DCCCCD and N O-DCCCCD are ntirely consistent with the normal isotopologues. Given the similarities between the most stable structures for OCS-HCCCCH with OCS-HCCH and for N O-HCCCCH with N O-HCCH, we conclude that diacetylene closely parallels acetylene upon complexation with OCS or N O. Acknowledgements
The financial support of the Natural Sciences and Engineering Research Council of Canada is gratefully acknowledged. The High Performance Computing department of the CINECA Supercomputer Centre (grant no. HP10C8R8EI) and the SCSCF (“Sistema per il Calcolo Scientifico di Ca′ Foscari”) facility are gratefully acknowledged for the utilization of computer resources. A.C.P. gratefully acknowledge the financial support of Università Ca’ Foscari Venezia (ADiR funds).
Appendix A. Supplementary data
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Observed and calculated transitions for OCS-HCCCCH in the region of the fundamental band of OCS (units of cm -1 ). ****************************************************************************** J' Ka' Kc' J" Ka" Kc" Observed Calculated Obs-Calc Weight ****************************************************************************** 9 5 5 10 6 4 2054.78574 2054.78454 0.00119 0.25 9 5 4 10 6 5 2054.78574 2054.78566 0.00007 0.25 7 6 1 8 7 2 2054.80586 2054.80560 0.00025 0.25 7 6 2 8 7 1 2054.80586 2054.80560 0.00025 0.25 9 4 6 10 5 5 2054.90163 2054.90135 0.00027 0.25 7 5 3 8 6 2 2054.92716 2054.92732 -0.00015 0.25 7 5 2 8 6 3 2054.92716 2054.92740 -0.00023 0.25 8 4 4 9 5 5 2054.98389 2054.98370 0.00018 1.00 6 5 2 7 6 1 2054.99872 2054.99886 -0.00014 0.25 6 5 1 7 6 2 2054.99872 2054.99887 -0.00015 0.25 6 5 1 7 6 2 2054.99872 2054.99887 -0.00015 0.25 6 5 2 7 6 1 2054.99872 2054.99886 -0.00014 0.25 7 4 4 8 5 3 2055.04882 2055.04872 0.00010 1.00 7 4 3 8 5 4 2055.05140 2055.05131 0.00009 1.00 5 5 1 6 6 0 2055.07068 2055.07044 0.00023 0.25 5 5 0 6 6 1 2055.07068 2055.07044 0.00023 0.25 6 4 2 7 5 3 2055.12095 2055.12124 -0.00028 0.25 6 4 3 7 5 2 2055.12095 2055.12052 0.00042 0.25 8 3 5 9 4 6 2055.14721 2055.14712 0.00008 1.00 7 3 5 8 4 4 2055.15611 2055.15621 -0.00009 1.00 5 4 1 6 5 2 2055.19192 2055.19223 -0.00031 0.25 5 4 2 6 5 1 2055.19192 2055.19209 -0.00017 0.25 7 3 4 8 4 5 2055.19521 2055.19534 -0.00013 1.00 6 3 4 7 4 3 2055.23641 2055.23653 -0.00011 1.00 6 3 3 7 4 4 2055.25275 2055.25291 -0.00015 1.00 4 4 0 5 5 1 2055.26320 2055.26362 -0.00042 0.25
4 4 1 5 5 0 2055.26320 2055.26361 -0.00040 0.25 6 2 5 7 3 4 2055.29749 2055.29772 -0.00022 1.00 5 3 3 6 4 2 2055.31161 2055.31191 -0.00029 1.00 5 3 2 6 4 3 2055.31750 2055.31748 0.00001 1.00 8 2 6 9 3 7 2055.36010 2055.36014 -0.00003 1.00 11 3 9 12 4 8 2055.36796 2055.36715 0.00080 1.00 5 1 5 6 2 4 2055.37112 2055.37133 -0.00020 1.00 11 3 8 12 2 11 2055.37506 2055.37462 0.00043 1.00 7 2 5 8 3 6 2055.39129 2055.39159 -0.00029 1.00 5 2 4 6 3 3 2055.40216 2055.40241 -0.00025 1.00 11 0 11 12 1 12 2055.43818 2055.43790 0.00027 0.25 11 1 11 12 0 12 2055.43818 2055.43814 0.00003 0.25 10 2 9 11 3 8 2055.44544 2055.44539 0.00004 1.00 3 3 0 4 4 1 2055.45660 2055.45688 -0.00028 0.25 3 3 1 4 4 0 2055.45660 2055.45668 -0.00008 0.25 5 2 3 6 3 4 2055.47156 2055.47185 -0.00029 1.00 9 1 8 10 2 9 2055.48121 2055.48133 -0.00011 1.00 4 2 3 5 3 2 2055.49264 2055.49289 -0.00025 1.00 10 1 10 11 0 11 2055.49706 2055.49710 -0.00004 0.25 10 0 10 11 1 11 2055.49706 2055.49658 0.00048 0.25 9 2 8 10 1 9 2055.51063 2055.51052 0.00011 1.00 4 2 2 5 3 3 2055.52359 2055.52391 -0.00031 1.00 8 1 7 9 2 8 2055.52909 2055.52920 -0.00010 1.00 8 2 7 9 1 8 2055.57994 2055.57996 -0.00002 1.00 3 2 1 4 3 2 2055.58407 2055.58425 -0.00017 1.00 8 1 8 9 0 9 2055.61533 2055.61541 -0.00007 1.00 8 1 8 9 0 9 2055.61541 2055.61541 0.00000 1.00 3 1 3 4 2 2 2055.63864 2055.63860 0.00004 1.00 2 2 1 3 3 0 2055.64887 2055.64891 -0.00003 1.00 7 2 6 8 1 7 2055.65504 2055.65542 -0.00037 1.00 7 0 7 8 1 8 2055.67033 2055.67035 -0.00002 1.00 7 1 7 8 0 8 2055.67517 2055.67520 -0.00003 1.00
10 2 9 10 3 8 2055.70243 2055.70254 -0.00011 1.00 10 3 8 10 4 7 2055.70452 2055.70451 0.00000 1.00 9 3 7 9 4 6 2055.72130 2055.72148 -0.00017 1.00 6 0 6 7 1 7 2055.72639 2055.72645 -0.00006 1.00 7 3 4 7 4 3 2055.76826 2055.76864 -0.00038 1.00 8 0 8 8 1 7 2055.77681 2055.77681 -0.00000 1.00 5 0 5 6 1 6 2055.78047 2055.78064 -0.00017 1.00 10 1 9 10 2 8 2055.78362 2055.78354 0.00008 1.00 2 1 1 3 2 2 2055.79137 2055.79139 -0.00002 1.00 5 1 5 6 0 6 2055.79864 2055.79879 -0.00014 1.00 7 2 6 7 3 5 2055.80888 2055.80889 -0.00000 1.00 5 2 4 6 1 5 2055.82692 2055.82657 0.00035 1.00 1 1 0 2 2 1 2055.84992 2055.84955 0.00036 1.00 4 1 4 5 0 5 2055.86473 2055.86454 0.00018 1.00 4 2 2 4 3 1 2055.88015 2055.87996 0.00019 1.00 5 2 3 5 3 2 2055.89600 2055.89603 -0.00003 1.00 2 0 2 3 1 3 2055.93210 2055.93187 0.00023 1.00 3 1 3 3 2 2 2055.94540 2055.94520 0.00019 1.00 7 1 6 7 2 5 2055.96164 2055.96176 -0.00011 1.00 5 0 5 5 1 4 2055.97204 2055.97218 -0.00014 1.00 1 0 1 2 1 2 2055.98462 2055.98455 0.00007 1.00 6 1 5 6 2 4 2055.99379 2055.99393 -0.00014 1.00 2 1 1 2 2 0 2056.00104 2056.00097 0.00006 1.00 2 1 2 3 0 3 2056.00820 2056.00808 0.00012 1.00 4 1 3 4 2 2 2056.01557 2056.01574 -0.00017 1.00 4 0 4 4 1 3 2056.02294 2056.02297 -0.00003 1.00 0 0 0 1 1 1 2056.04269 2056.04261 0.00008 1.00 3 0 3 3 1 2 2056.06072 2056.06081 -0.00009 1.00 1 0 1 1 1 0 2056.10038 2056.10049 -0.00011 1.00 1 1 0 1 0 1 2056.23532 2056.23551 -0.00019 1.00 2 1 1 2 0 2 2056.24956 2056.24975 -0.00019 1.00 3 1 2 3 0 3 2056.27402 2056.27431 -0.00029 1.00
1 1 1 0 0 0 2056.29430 2056.29350 0.00079 1.00 1 1 1 0 0 0 2056.29430 2056.29350 0.00079 1.00 1 1 1 0 0 0 2056.29430 2056.29350 0.00079 1.00 4 1 3 4 0 4 2056.31152 2056.31146 0.00005 1.00 4 2 2 4 1 3 2056.31873 2056.31866 0.00006 1.00 3 2 1 3 1 2 2056.32431 2056.32431 0.00000 1.00 3 0 3 2 1 2 2056.32748 2056.32735 0.00013 1.00 2 2 0 2 1 1 2056.33499 2056.33473 0.00026 1.00 6 2 4 6 1 5 2056.33845 2056.33845 -0.00000 1.00 2 1 2 1 0 1 2056.35146 2056.35131 0.00015 1.00 5 1 4 5 0 5 2056.36143 2056.36140 0.00003 1.00 7 2 5 7 1 6 2056.36954 2056.36939 0.00015 1.00 3 2 2 3 1 3 2056.39009 2056.39002 0.00007 1.00 8 3 5 8 2 6 2056.39469 2056.39451 0.00018 1.00 4 0 4 3 0 3 2056.43246 2056.43235 0.00010 1.00 5 3 2 5 2 3 2056.43745 2056.43758 -0.00012 1.00 5 2 4 5 1 5 2056.44988 2056.44984 0.00004 1.00 5 0 5 4 1 4 2056.46968 2056.46959 0.00009 1.00 5 1 5 4 0 4 2056.50167 2056.50172 -0.00005 1.00 6 1 5 5 2 4 2056.50626 2056.50648 -0.00021 1.00 7 3 5 7 2 6 2056.52256 2056.52255 0.00000 1.00 6 0 6 5 1 5 2056.53447 2056.53447 0.00000 1.00 8 4 4 8 3 5 2056.54053 2056.54061 -0.00007 1.00 8 4 4 8 3 5 2056.54053 2056.54061 -0.00007 1.00 8 4 4 8 3 5 2056.54053 2056.54061 -0.00007 1.00 3 2 2 2 1 1 2056.54412 2056.54405 0.00007 1.00 3 2 2 2 1 1 2056.54412 2056.54405 0.00007 1.00 3 2 2 2 1 1 2056.54412 2056.54405 0.00007 1.00 8 3 6 8 2 7 2056.54984 2056.54983 0.00000 1.00 8 3 6 8 2 7 2056.54984 2056.54983 0.00000 1.00 8 3 6 8 2 7 2056.54984 2056.54983 0.00000 1.00 6 1 6 5 0 5 2056.55276 2056.55260 0.00015 1.00
7 4 3 7 3 4 2056.56282 2056.56280 0.00002 1.00 8 2 6 7 3 5 2056.56882 056.569097 -0.00026 1.00 6 4 2 6 3 3 2056.57806 2056.57818 -0.00011 1.00 5 4 1 5 3 2 2056.58687 2056.58725 -0.00038 1.00 7 1 7 6 0 6 2056.60589 2056.60576 0.00012 1.00 9 2 8 9 1 9 2056.63641 2056.63631 0.00009 1.00 5 2 4 4 1 3 2056.64049 2056.64040 0.00008 1.00 8 0 8 7 1 7 2056.65586 2056.65583 0.00002 1.00 8 1 8 7 0 7 2056.66063 2056.66067 -0.00004 1.00 6 2 5 5 1 4 2056.68088 2056.68096 -0.00008 1.00 3 3 1 2 2 0 2056.68476 2056.68458 0.00017 1.00 3 3 1 2 2 0 2056.68476 2056.68458 0.00017 1.00 3 3 0 2 2 1 2056.68655 2056.68667 -0.00012 1.00 3 3 0 2 2 1 2056.68655 2056.68667 -0.00012 1.00 4 2 2 3 1 3 2056.69637 2056.69623 0.00013 1.00 8 5 3 8 4 4 2056.70012 2056.70008 0.00003 1.00 9 0 9 8 1 8 2056.71423 2056.71428 -0.00005 1.00 9 1 9 8 0 8 2056.71641 2056.71665 -0.00023 1.00 7 2 6 6 1 5 2056.71895 2056.71918 -0.00023 1.00 8 2 7 7 1 6 2056.75793 2056.75804 -0.00010 1.00 4 3 1 3 2 2 2056.76120 2056.76120 -0.00000 1.00 10 0 10 9 1 9 2056.77257 2056.77205 0.00052 0.25 10 1 10 9 0 9 2056.77257 2056.77317 -0.00060 0.25 9 2 8 8 1 7 2056.80010 2056.80009 0.00000 1.00 5 3 3 4 2 2 2056.81014 2056.81019 -0.00005 1.00 10 1 9 9 2 8 2056.81691 2056.81725 -0.00034 1.00 11 1 11 10 0 10 2056.82965 2056.82996 -0.00030 0.25 11 0 11 10 1 10 2056.82965 2056.82943 0.00021 0.25 10 2 9 9 1 8 2056.84647 2056.84642 0.00004 1.00 6 3 4 5 2 3 2056.86120 2056.86123 -0.00003 1.00 12 1 12 11 0 11 2056.88645 2056.88682 -0.00037 0.25 12 0 12 11 1 11 2056.88645 2056.88658 -0.00013 0.25
11 2 10 10 1 9 2056.89657 2056.89662 -0.00004 1.00 7 3 5 6 2 4 2056.90371 2056.90373 -0.00002 1.00 6 3 3 5 2 4 2056.93080 2056.93073 0.00007 1.00 8 3 6 7 2 5 2056.93892 2056.93894 -0.00002 1.00 12 3 9 11 2 10 2056.94087 2056.94120 -0.00033 1.00 9 3 7 8 2 6 2056.96887 2056.96887 -0.00000 1.00 10 3 8 9 2 7 2056.99650 2056.99621 0.00029 1.00 14 0 14 13 1 13 2057.00025 2057.00048 -0.00022 0.25 14 1 14 13 0 13 2057.00025 2057.00053 -0.00027 0.25 13 2 12 12 3 9 2057.00415 2057.00426 -0.00011 1.00 6 4 3 5 3 2 2057.01575 2057.01584 -0.00008 1.00 6 4 2 5 3 3 2057.02139 2057.02142 -0.00003 1.00 11 3 9 10 2 8 2057.02495 2057.02417 0.00077 1.00 5 5 0 4 4 1 2057.07104 2057.07097 0.00006 0.25 5 5 1 4 4 0 2057.07104 2057.07096 0.00008 0.25 7 4 4 6 3 3 2057.07910 2057.07921 -0.00010 1.00 7 4 3 6 3 4 2057.09541 2057.09562 -0.00020 1.00 16 2 14 15 1 15 2057.11431 2057.11399 0.00031 0.25 16 1 16 15 2 13 2057.11431 2057.11400 0.00030 0.25 8 4 5 7 3 4 2057.13517 2057.13538 -0.00020 1.00 6 5 2 5 4 1 2057.14135 2057.14136 -0.00000 0.25 6 5 1 5 4 2 2057.14135 2057.14150 -0.00015 0.25 8 3 5 7 2 6 2057.15555 2057.15565 -0.00010 1.00 9 4 6 8 3 5 2057.18222 2057.18201 0.00021 0.25 7 5 2 6 4 3 2057.21133 2057.21189 -0.00056 0.25 7 5 3 6 4 2 2057.21133 2057.21118 0.00015 0.25 6 6 0 5 5 1 2057.26372 2057.26347 0.00025 0.25 6 6 1 5 5 0 2057.26372 2057.26346 0.00025 0.25 8 5 4 7 4 3 2057.27946 2057.27974 -0.00027 1.00 8 5 3 7 4 4 2057.28250 2057.28233 0.00016 1.00 7 6 2 6 5 1 2057.33372 2057.33386 -0.00014 0.25 7 6 1 6 5 2 2057.33372 2057.33388 -0.00015 0.25
9 5 5 8 4 4 2057.34601 2057.34578 0.00023 0.25 9 5 4 8 4 5 2057.35372 2057.35342 0.00029 0.25 8 6 2 7 5 3 2057.40446 2057.40406 0.00039 0.25 8 6 3 7 5 2 2057.40446 2057.40399 0.00047 0.25 13 6 8 12 5 7 2057.73328 2057.73461 -0.00133 0.00 10 7 3 11 8 4 2054.46520 2054.46885 -0.00365 0.00 10 7 4 11 8 3 2054.46520 2054.46884 -0.00364 0.00 11 7 4 12 8 5 2054.39494 2054.39724 -0.00230 0.00 11 7 5 12 8 4 2054.39494 2054.39722 -0.00228 0.00 12 7 5 13 8 6 2054.32388 2054.32583 -0.00195 0.00 12 7 6 13 8 5 2054.32388 2054.32578 -0.00190 0.00 12 7 5 11 6 6 2057.80230 2057.80476 -0.00245 0.00 12 7 6 11 6 5 2057.80230 2057.80429 -0.00199 0.00 13 7 6 14 8 7 2054.25311 2054.25477 -0.00166 0.00 13 7 7 14 8 6 2054.25311 2054.25459 -0.00148 0.00 9 8 1 8 7 2 2057.71409 2057.71834 -0.00424 0.00 9 8 2 8 7 1 2057.71409 2057.71834 -0.00424 0.00 9 8 1 10 9 2 2054.41467 2054.41912 -0.00445 0.00 9 8 2 10 9 1 2054.41467 2054.41912 -0.00445 0.00 10 8 2 9 7 3 2057.78517 2057.78840 -0.00323 0.00 10 8 3 9 7 2 2057.78517 2057.78840 -0.00323 0.00 10 8 2 11 9 3 2054.34389 2054.34725 -0.00336 0.00 10 8 3 11 9 2 2054.34389 2054.34725 -0.00336 0.00 11 8 3 10 7 4 2057.85517 2057.85823 -0.00305 0.00 11 8 4 10 7 3 2057.85517 2057.85823 -0.00305 0.00 11 8 3 12 9 4 2054.27241 2054.27539 -0.00298 0.00 11 8 4 12 9 3 2054.27241 2054.27539 -0.00298 0.00 12 8 4 11 7 5 2057.92511 2057.92777 -0.00265 0.00 12 8 5 11 7 4 2057.92511 2057.92776 -0.00264 0.00 12 8 4 13 9 5 2054.20064 2054.20360 -0.00296 0.00 12 8 5 13 9 4 2054.20064 2054.20359 -0.00295 0.00 13 8 5 12 7 6 2057.99424 2057.99694 -0.00270 0.00
13 8 6 12 7 5 2057.99424 2057.99689 -0.00264 0.00 9 9 0 8 8 1 2057.83664 2057.84024 -0.00359 0.00 9 9 1 8 8 0 2057.83664 2057.84024 -0.00359 0.00 9 9 0 10 10 1 2054.29437 2054.29783 -0.00346 0.00 9 9 1 10 10 0 2054.29437 2054.29783 -0.00346 0.00 10 9 1 9 8 2 2057.90713 2057.91037 -0.00323 0.00 10 9 2 9 8 1 2057.90713 2057.91037 -0.00323 0.00 10 9 1 11 10 2 2054.22240 2054.22592 -0.00352 0.00 10 9 2 11 10 1 2054.22240 2054.22592 -0.00352 0.00 11 9 2 10 8 3 2057.97724 2057.98034 -0.00310 0.00 11 9 3 10 8 2 2057.97724 2057.98034 -0.00310 0.00 13 9 4 14 10 5 2054.00690 2054.01007 -0.00317 0.00 13 9 5 14 10 4 2054.00690 2054.01007 -0.00317 0.00 11 10 1 10 9 2 2058.09945 2058.10225 -0.00279 0.00 11 10 2 10 9 1 2058.09945 2058.10225 -0.00279 0.00 11 10 1 12 11 2 2054.03009 2054.03277 -0.00268 0.00 11 10 2 12 11 1 2054.03009 2054.03277 -0.00268 0.00 12 10 2 11 9 3 2058.16962 2058.17213 -0.00250 0.00 12 10 3 11 9 2 2058.16962 2058.17213 -0.00250 0.00 13 10 3 12 9 4 2058.23988 2058.24184 -0.00196 0.00 13 10 4 12 9 3 2058.23988 2058.24184 -0.00196 0.00 14 10 4 13 9 5 2058.30437 2058.31134 -0.00697 0.00 14 10 5 13 9 4 2058.30437 2058.31134 -0.00697 0.00 11 11 0 10 10 1 2058.22057 2058.22406 -0.00348 0.00 11 11 1 10 10 0 2058.22057 2058.22406 -0.00348 0.00 12 11 1 11 10 2 2058.29059 2058.29397 -0.00337 0.00 12 11 2 11 10 1 2058.29059 2058.29397 -0.00337 0.00 ******************************************************************************
Table A-2. Observed and calculated transitions for OCS-DCCCCD in the region of the fundamental band of OCS (units of cm -1 ). ****************************************************************************** J' Ka' Kc' J" Ka" Kc" Observed Calculated Obs-Calc Weight **************************************************************************** 11 5 6 12 6 7 2054.55716 2054.55717 -0.00001 1.00 9 6 3 10 7 4 2054.57229 2054.57229 -0.00000 0.25 9 6 4 10 7 3 2054.57229 2054.57224 0.00005 0.25 7 7 0 8 8 1 2054.59903 2054.59874 0.00028 0.25 7 7 1 8 8 0 2054.59903 2054.59874 0.00028 0.25 10 5 6 11 6 5 2054.61494 2054.61503 -0.00009 1.00 8 6 2 9 7 3 2054.64101 2054.64100 0.00001 0.25 8 6 3 9 7 2 2054.64101 2054.64099 0.00002 0.25 7 6 1 8 7 2 2054.70992 2054.70987 0.00004 0.25 7 6 2 8 7 1 2054.70992 2054.70987 0.00005 0.25 8 5 3 9 6 4 2054.75274 2054.75293 -0.00018 0.25 8 5 4 9 6 3 2054.75274 2054.75247 0.00027 0.25 10 4 6 11 5 7 2054.76227 2054.76242 -0.00014 1.00 6 6 0 7 7 1 2054.77895 2054.77881 0.00013 0.25 6 6 1 7 7 0 2054.77895 2054.77881 0.00013 0.25 7 5 2 8 6 3 2054.82113 2054.82124 -0.00011 0.25 7 5 3 8 6 2 2054.82113 2054.82114 -0.00000 0.25 9 4 6 10 5 5 2054.78812 2054.78808 0.00004 1.00 6 5 1 7 6 2 2054.89003 2054.88996 0.00007 0.25 6 5 2 7 6 1 2054.89003 2054.88994 0.00009 0.25 7 4 4 8 5 3 2054.93185 2054.93173 0.00012 1.00 5 5 0 6 6 1 2054.95901 2054.95883 0.00018 0.25 5 5 1 6 6 0 2054.95901 2054.95883 0.00018 0.25 5 4 1 6 5 2 2055.07020 2055.07010 0.00009 0.25 5 4 2 6 5 1 2055.07020 2055.06992 0.00027 0.25
12 4 8 13 3 11 2055.09382 2055.09400 -0.00018 1.00 6 3 3 7 4 4 2055.12487 2055.12454 0.00032 1.00 4 4 0 5 5 1 2055.13889 2055.13882 0.00006 0.25 4 4 1 5 5 0 2055.13889 2055.13880 0.00009 0.25 5 3 3 6 4 2 2055.17885 2055.17868 0.00016 0.25 5 3 2 6 4 3 2055.18534 2055.18533 0.00000 0.25 9 2 7 10 3 8 2055.19955 2055.19957 -0.00002 1.00 10 1 9 11 2 10 2055.28005 2055.27936 0.00068 1.00 11 0 11 12 1 12 2055.28591 2055.28556 0.00034 0.25 11 1 11 12 0 12 2055.28591 2055.28570 0.00020 0.25 3 3 0 4 4 1 2055.31860 2055.31887 -0.00027 0.25 3 3 1 4 4 0 2055.31860 2055.31863 -0.00003 0.25 10 0 10 11 1 11 2055.34159 2055.34140 0.00018 0.25 10 1 10 11 0 11 2055.34159 2055.34173 -0.00014 0.25 4 2 3 5 3 2 2055.34514 2055.34527 -0.00013 1.00 9 0 9 10 1 10 2055.39754 2055.39709 0.00044 0.25 9 1 9 10 0 10 2055.39754 2055.39782 -0.00028 0.25 8 2 7 9 1 8 2055.41435 2055.41467 -0.00032 1.00 3 2 2 4 3 1 2055.42416 2055.42453 -0.00037 1.00 3 2 1 4 3 2 2055.43607 2055.43604 0.00002 1.00 6 1 5 7 2 6 2055.45954 2055.45964 -0.00010 1.00 7 0 7 8 1 8 2055.50741 2055.50738 0.00002 0.25 7 1 7 8 0 8 2055.51002 2055.51079 -0.00077 0.25 6 0 6 7 1 7 2055.56121 2055.56129 -0.00008 0.25 6 2 5 7 1 6 2055.56121 2055.56063 0.00057 0.25 1 1 0 1 0 1 2056.04460 2056.04444 0.00016 1.00 2 1 1 2 0 2 2056.05888 2056.05888 -0.00000 1.00 2 0 2 1 1 1 2056.06663 2056.06658 0.00004 1.00 1 1 1 0 0 0 2056.09997 2056.09997 -0.00000 1.00 4 1 3 5 2 4 2055.53668 2055.53666 0.00001 1.00 11 3 8 11 2 9 2055.53325 2055.53289 0.00035 1.00 6 1 6 7 0 7 2055.56817 2055.56836 -0.00019 1.00
9 3 7 9 4 6 2055.57106 2055.57128 -0.00022 1.00 4 2 2 4 1 3 2056.11979 2056.11961 0.00018 1.00 3 0 3 2 1 2 2056.13946 2056.13899 0.00046 1.00 2 2 0 2 1 1 2056.13315 2056.13312 0.00003 1.00 6 2 4 6 1 5 2056.14468 2056.14491 -0.00022 1.00 2 1 2 1 0 1 2056.15536 2056.15540 -0.00004 1.00 2 2 1 2 1 2 2056.16830 2056.16850 -0.00020 1.00 5 1 4 5 0 5 2056.17220 2056.17223 -0.00003 1.00 7 2 5 7 1 6 2056.17954 2056.17930 0.00024 1.00 8 3 5 8 2 6 2056.18999 2056.19003 -0.00003 1.00 7 3 4 7 2 5 2056.19231 2056.19265 -0.00034 1.00 5 3 2 5 4 1 2055.59985 2055.59995 -0.00010 1.00 5 0 5 6 1 6 2055.61391 2055.61357 0.00033 1.00 5 2 4 6 1 5 2055.64359 2055.64386 -0.00027 1.00 4 0 4 5 1 5 2055.66344 2055.66358 -0.00014 1.00 7 0 7 7 1 6 2055.66677 2055.66698 -0.00021 1.00 6 1 6 6 2 5 2055.67429 2055.67481 -0.00052 1.00 5 1 5 5 2 4 2055.71450 2055.71495 -0.00045 1.00 4 2 2 4 3 1 2055.72270 2055.72267 0.00002 1.00 5 2 3 5 3 2 2055.73871 2055.73906 -0.00035 1.00 4 1 4 4 2 3 2055.74874 2055.74885 -0.00011 1.00 5 0 5 5 1 4 2055.79150 2055.79111 0.00038 1.00 2 1 2 2 2 1 2055.79590 2055.79598 -0.00008 1.00 1 0 1 2 1 2 2055.80963 2055.80922 0.00040 1.00 6 1 5 6 2 4 2055.81790 2055.81758 0.00032 1.00 3 2 2 4 1 3 2055.82091 2055.82148 -0.00056 1.00 2 1 2 3 0 3 2055.82577 2055.82540 0.00037 1.00 2 1 1 2 2 0 2055.83157 2055.83132 0.00025 1.00 0 0 0 1 1 1 2055.86479 2055.86479 -0.00000 1.00 4 4 1 3 3 0 2056.64492 2056.64482 0.00009 0.25 4 4 0 3 3 1 2056.64492 2056.64506 -0.00014 0.25 7 4 3 6 3 4 2056.85729 2056.85681 0.00047 1.00
6 4 3 5 3 2 2056.77731 2056.77727 0.00003 1.00 9 6 3 8 5 4 2057.20685 2057.20707 -0.00022 0.25 9 6 4 8 5 3 2057.20685 2057.20661 0.00023 0.25 7 7 0 6 6 1 2057.18208 2057.18218 -0.00010 0.25 7 7 1 6 6 0 2057.18208 2057.18218 -0.00010 0.25 10 5 6 9 4 5 2057.14631 2057.14616 0.00014 0.25 10 4 6 9 3 7 2057.12740 2057.12777 -0.00037 0.25 9 5 4 8 4 5 2057.09857 2057.09859 -0.00002 1.00 7 6 1 6 5 2 2057.07136 2057.07142 -0.00006 0.25 7 6 2 6 5 1 2057.07136 2057.07140 -0.00004 0.25 10 8 2 9 7 3 2057.49658 2057.49662 -0.00004 0.25 10 8 3 9 7 2 2057.49658 2057.49662 -0.00004 0.25 9 8 1 8 7 2 2057.42877 2057.42883 -0.00006 0.25 9 8 2 8 7 1 2057.42877 2057.42883 -0.00006 0.25 10 7 3 9 6 4 2057.38581 2057.38574 0.00006 0.25 10 7 4 9 6 3 2057.38581 2057.38568 0.00012 0.25 8 8 0 7 7 1 2057.36076 2057.36088 -0.00012 0.25 8 8 1 7 7 0 2057.36076 2057.36088 -0.00012 0.25 11 6 5 10 5 6 2057.34179 2057.34220 -0.00041 1.00 9 7 2 8 6 3 2057.31803 2057.31811 -0.00008 0.25 9 7 3 8 6 2 2057.31803 2057.31810 -0.00007 0.25 13 5 9 12 2 10 2057.25971 2057.25985 -0.00014 1.00 11 5 7 10 4 6 2057.19538 2057.19515 0.00022 1.00 8 5 3 7 4 4 2057.02941 2057.02911 0.00029 1.00 14 4 11 13 1 12 2057.04275 2057.04245 0.00029 1.00 8 6 2 7 5 3 2057.13926 2057.13937 -0.00011 0.25 8 6 3 7 5 2 2057.13926 2057.13926 -0.00000 0.25 11 4 8 10 3 7 2056.98823 2056.98815 0.00007 1.00 6 6 0 5 5 1 2057.00303 2057.00327 -0.00024 0.25 6 6 1 5 5 0 2057.00303 2057.00327 -0.00024 0.25 7 5 3 6 4 2 2056.96040 2056.95975 0.00064 0.25 7 5 2 6 4 3 2056.96040 2056.96068 -0.00028 0.25
8 4 4 7 3 5 2056.93556 2056.93548 0.00007 0.25 8 3 5 7 2 6 2056.93556 2056.93502 0.00053 0.25 9 4 6 8 3 5 2056.93181 2056.93174 0.00006 1.00 6 5 2 5 4 1 2056.89257 2056.89228 0.00028 0.25 6 5 1 5 4 2 2056.89257 2056.89247 0.00009 0.25 8 4 5 7 3 4 2056.88966 2056.88950 0.00015 1.00 10 3 8 9 2 7 2056.76016 2056.75982 0.00033 1.00 13 1 13 12 0 12 2056.72816 2056.72838 -0.00022 0.25 13 0 13 12 1 12 2056.72816 2056.72832 -0.00016 0.25 11 2 10 10 1 9 2056.67985 2056.67972 0.00012 1.00 11 3 8 10 2 9 2056.66947 2056.66913 0.00033 1.00 11 1 11 10 0 10 2056.61810 2056.61849 -0.00039 0.25 11 0 11 10 1 10 2056.61810 2056.61817 -0.00007 0.25 10 1 9 9 2 8 2056.60957 2056.60950 0.00006 1.00 10 1 10 9 0 9 2056.56307 2056.56363 -0.00056 0.25 10 0 10 9 1 9 2056.56307 2056.56291 0.00015 0.25 4 3 2 3 2 1 2056.52788 2056.52779 0.00008 1.00 8 1 7 7 2 6 2056.47694 2056.47739 -0.00045 1.00 9 1 8 8 2 7 2056.54552 2056.54619 -0.00067 1.00 8 1 8 7 0 7 2056.45488 2056.45477 0.00010 1.00 8 0 8 7 1 7 2056.45132 2056.45136 -0.00004 1.00 9 4 6 9 3 7 2056.38848 2056.38849 -0.00001 1.00 7 1 7 6 0 6 2056.40113 2056.40146 -0.00033 0.25 7 1 6 6 2 5 2056.40113 2056.40167 -0.00054 0.25 6 4 2 6 3 3 2056.35278 2056.35309 -0.00031 1.00 6 1 6 5 0 5 2056.34946 2056.34970 -0.00024 1.00 5 0 5 4 1 4 2056.27446 2056.27422 0.00024 1.00 3 3 1 3 2 2 2056.26223 2056.26246 -0.00023 1.00 5 2 4 5 1 5 2056.24839 2056.24843 -0.00004 1.00 8 2 6 8 1 7 2056.22874 2056.22859 0.00015 1.00 4 2 3 4 1 4 2056.21514 2056.21498 0.00015 1.00 4 0 4 3 1 3 2056.20858 2056.20875 -0.00016 1.00
9 3 6 9 2 7 2056.20198 2056.20220 -0.00021 1.00 1 0 1 1 1 0 2055.92063 2055.92026 0.00036 1.00 2 0 2 2 1 1 2055.90586 2055.90561 0.00024 1.00 3 0 3 3 1 2 2055.88088 2055.88024 0.00064 1.00 7 1 6 7 2 5 2055.78206 2055.78248 -0.00042 1.00 3 1 3 3 2 2 2055.77564 2055.77593 -0.00029 1.00 ****************************************************************************** Table A-3. Observed and calculated transitions for N O-HCCCH in the region of the fundamental band of N O (in units of cm -1 ). ****************************************************************************** J' Ka' Kc' J" Ka" Kc" Observed Calculated Obs-Calc Weight **************************************************************************** 8 7 1 9 8 2 2223.65138 2223.65179 -0.00041 0.25 8 7 2 9 8 1 2223.65138 2223.65179 -0.00041 0.25 7 7 1 8 8 0 2223.73462 2223.73466 -0.00004 0.25 7 7 0 8 8 1 2223.73462 2223.73466 -0.00004 0.25 10 5 6 11 6 5 2223.93132 2223.93177 -0.00045 0.25 10 5 5 11 6 6 2223.93132 2223.93197 -0.00065 0.25 7 6 2 8 7 1 2223.95739 2223.95735 0.00004 0.25 7 6 1 8 7 2 2223.95739 2223.95735 0.00004 0.25 9 5 4 10 6 5 2224.01392 2224.01420 -0.00028 0.25 9 5 5 10 6 4 2224.01392 2224.01413 -0.00021 0.25 8 5 4 9 6 3 2224.09656 2224.09675 -0.00018 0.25 8 5 3 9 6 4 2224.09656 2224.09677 -0.00020 0.25 7 5 2 8 6 3 2224.17925 2224.17956 -0.00030 0.25 7 5 3 8 6 2 2224.17925 2224.17955 -0.00030 0.25 6 5 1 7 6 2 2224.26267 2224.26248 0.00019 0.25 6 5 2 7 6 1 2224.26267 2224.26248 0.00019 0.25
8 4 4 9 5 5 2224.31880 2224.31958 -0.00077 0.25 8 4 5 9 5 4 2224.31880 2224.31865 0.00014 0.25 5 5 0 6 6 1 2224.34583 2224.34548 0.00035 0.25 5 5 1 6 6 0 2224.34583 2224.34548 0.00035 0.25 6 4 2 7 5 3 2224.48427 2224.48417 0.00009 0.25 6 4 3 7 5 2 2224.48427 2224.48409 0.00018 0.25 8 3 6 9 4 5 2224.53313 2224.53329 -0.00015 1.00 4 4 0 5 5 1 2224.65028 2224.65004 0.00024 0.25 4 4 1 5 5 0 2224.65028 2224.65004 0.00024 0.25 8 2 7 9 3 6 2224.67479 2224.67467 0.00011 1.00 6 3 4 7 4 3 2224.70375 2224.70388 -0.00013 1.00 6 3 3 7 4 4 2224.70755 2224.70775 -0.00019 1.00 5 3 2 6 4 3 2224.78805 2224.78875 -0.00070 0.25 5 3 3 6 4 2 2224.78805 2224.78747 0.00058 0.25 9 2 7 10 3 8 2224.80968 2224.80981 -0.00012 1.00 11 5 6 11 6 5 2224.85303 2224.85186 0.00116 1.00 4 3 1 5 4 2 2224.87090 2224.87101 -0.00010 0.25 4 3 2 5 4 1 2224.87090 2224.87069 0.00021 0.25 6 2 5 7 3 4 2224.89668 2224.89693 -0.00025 1.00 7 2 5 8 3 6 2224.90338 2224.90342 -0.00004 1.00 3 3 1 4 4 0 2224.95399 2224.95380 0.00018 0.25 3 3 0 4 4 1 2224.95399 2224.95385 0.00014 0.25 6 2 4 7 3 5 2224.96127 2224.96114 0.00013 1.00 5 2 4 6 3 3 2224.99364 2224.99374 -0.00010 1.00 13 0 13 14 1 14 2225.00922 2225.00769 0.00152 0.25 13 1 13 14 0 14 2225.00922 2225.00969 -0.00047 0.25 4 2 2 5 3 3 2225.09870 2225.09873 -0.00003 1.00 3 2 1 4 3 2 2225.17593 2225.17627 -0.00034 1.00 10 0 10 11 1 11 2225.22035 2225.22048 -0.00012 1.00 10 1 10 11 0 11 2225.22991 2225.22988 0.00002 1.00 2 2 0 3 3 1 2225.25661 2225.25718 -0.00057 0.25 2 2 1 3 3 0 2225.25661 2225.25625 0.00035 0.25
6 1 5 7 2 6 2225.26118 2225.26150 -0.00032 1.00 9 1 9 10 0 10 2225.30499 2225.30486 0.00013 1.00 5 1 4 6 2 5 2225.31179 2225.31202 -0.00023 1.00 8 0 8 9 1 9 2225.35692 2225.35704 -0.00011 1.00 8 1 8 9 1 9 2225.37214 2225.37180 0.00033 1.00 7 3 5 8 3 6 2225.37679 2225.37723 -0.00043 1.00 8 1 8 9 0 9 2225.38138 2225.38138 0.00000 1.00 7 0 7 8 1 8 2225.42222 2225.42241 -0.00019 1.00 3 1 2 4 2 3 2225.42703 2225.42715 -0.00012 1.00 7 1 7 8 0 8 2225.46038 2225.46009 0.00028 1.00 6 0 6 7 1 7 2225.48526 2225.48536 -0.00010 1.00 6 2 5 6 3 4 2225.48900 2225.48944 -0.00043 1.00 2 1 1 3 2 2 2225.49287 2225.49287 0.00000 1.00 4 2 2 4 3 1 2225.51453 2225.51461 -0.00008 1.00 6 1 6 7 1 7 2225.51875 2225.51868 0.00006 1.00 5 0 5 6 0 6 2225.57996 2225.57991 0.00004 1.00 8 2 6 8 3 5 2225.58605 2225.58583 0.00021 1.00 5 1 5 6 1 6 2225.59292 2225.59290 0.00002 1.00 6 1 6 6 2 5 2225.59977 2225.59967 0.00009 1.00 4 0 4 5 1 5 2225.60561 2225.60546 0.00014 1.00 4 1 3 5 1 4 2225.61265 2225.61256 0.00009 1.00 4 2 2 5 2 3 2225.62060 2225.62047 0.00013 1.00 8 0 8 8 1 7 2225.64611 2225.64571 0.00039 1.00 4 0 4 5 0 5 2225.65296 2225.65291 0.00005 1.00 10 1 9 10 2 8 2225.68326 2225.68259 0.00067 0.25 10 1 9 10 2 8 2225.68326 2225.68259 0.00067 0.25 3 1 3 3 2 2 2225.68968 2225.68947 0.00020 1.00 3 1 2 4 1 3 2225.69874 2225.69856 0.00018 1.00 2 1 1 2 2 0 2225.74070 2225.74014 0.00055 1.00 3 1 3 4 1 4 2225.74337 2225.74322 0.00015 1.00 3 1 2 3 2 1 2225.75381 2225.75299 0.00082 0.25 3 1 2 3 2 1 2225.75381 2225.75299 0.00082 0.25
8 1 7 8 2 6 2225.75635 2225.75599 0.00035 0.25 8 1 7 8 2 6 2225.75635 2225.75599 0.00035 0.25 4 1 3 4 2 2 2225.76614 2225.76583 0.00031 1.00 1 0 1 2 1 2 2225.79369 2225.79355 0.00014 1.00 2 1 2 3 1 3 2225.81918 2225.81933 -0.00015 1.00 0 0 0 1 1 1 2225.86480 2225.86501 -0.00021 1.00 4 0 4 4 1 3 2225.87445 2225.87490 -0.00044 1.00 1 0 1 2 0 2 2225.88606 2225.88620 -0.00013 1.00 3 0 3 3 1 2 2225.90388 2225.90424 -0.00036 1.00 2 0 2 2 1 1 2225.92405 2225.92419 -0.00014 1.00 1 0 1 1 1 0 2225.93642 2225.93642 -0.00000 1.00 3 2 1 3 2 2 2226.05264 2226.05259 0.00004 0.25 7 3 4 7 3 5 2226.05264 2226.05364 -0.00099 0.25 1 0 1 0 0 0 2226.13349 2226.13347 0.00001 1.00 1 1 0 1 0 1 2226.16425 2226.16450 -0.00024 1.00 2 1 1 2 0 2 2226.17649 2226.17664 -0.00015 1.00 3 1 2 3 0 3 2226.19634 2226.19643 -0.00009 1.00 5 1 4 5 0 5 2226.26530 2226.26546 -0.00015 1.00 3 1 3 2 1 2 2226.28063 2226.28060 0.00003 1.00 3 2 1 2 2 0 2226.29982 2226.29987 -0.00005 1.00 2 1 2 1 0 1 2226.30713 2226.30724 -0.00010 1.00 4 2 2 4 1 3 2226.33238 2226.33245 -0.00006 1.00 8 2 6 8 1 7 2226.34160 2226.34159 0.00001 1.00 3 2 1 3 1 2 2226.34524 2226.34536 -0.00011 1.00 2 2 1 2 1 2 2226.39118 2226.39123 -0.00004 1.00 4 1 3 3 1 2 2226.40149 2226.40160 -0.00010 1.00 3 2 2 3 1 3 2226.40890 2226.40861 0.00029 1.00 10 2 8 10 1 9 2226.41372 2226.41364 0.00007 1.00 4 1 4 3 0 3 2226.43526 2226.43504 0.00022 1.00 5 0 5 4 0 4 2226.44760 2226.44751 0.00009 1.00 8 1 7 8 0 8 2226.45220 2226.45202 0.00017 1.00 6 0 6 5 1 5 2226.47244 2226.47234 0.00010 1.00
5 2 3 4 2 2 2226.47626 2226.47602 0.00024 1.00 6 0 6 5 0 5 2226.51996 2226.51978 0.00017 1.00 2 2 1 1 1 0 2226.53431 2226.53410 0.00020 1.00 6 1 6 5 0 5 2226.55302 2226.55311 -0.00008 1.00 7 0 7 6 1 6 2226.55645 2226.55654 -0.00009 1.00 6 1 5 5 1 4 2226.57185 2226.57171 0.00013 1.00 5 3 3 5 2 4 2226.59617 2226.59571 0.00046 1.00 7 2 6 6 2 5 2226.61935 2226.61978 -0.00042 1.00 8 0 8 7 1 7 2226.63751 2226.63718 0.00032 1.00 3 2 1 2 1 2 2226.64379 2226.64371 0.00007 1.00 4 2 3 3 1 2 2226.67106 2226.67104 0.00001 1.00 8 1 8 7 0 7 2226.67504 2226.67497 0.00006 1.00 9 1 9 8 0 8 2226.73920 2226.73922 -0.00002 1.00 6 2 5 5 1 4 2226.78573 2226.78568 0.00004 1.00 10 0 10 9 1 9 2226.78977 2226.79008 -0.00030 1.00 10 1 10 9 0 9 2226.80526 2226.80544 -0.00017 1.00 11 0 11 10 1 10 2226.86323 2226.86370 -0.00046 1.00 4 3 1 3 2 2 2226.92169 2226.92174 -0.00005 1.00 5 3 3 4 2 2 2226.99444 2226.99454 -0.00009 1.00 6 3 4 5 2 3 2227.06689 2227.06671 0.00018 1.00 6 3 3 5 2 4 2227.09924 2227.09923 0.00000 1.00 4 4 1 3 3 0 2227.13235 2227.13224 0.00010 0.25 4 4 0 3 3 1 2227.13235 2227.13229 0.00005 0.25 5 4 1 4 3 2 2227.21530 2227.21529 0.00001 0.25 5 4 2 4 3 1 2227.21530 2227.21497 0.00032 0.25 6 4 3 5 3 2 2227.29774 2227.29712 0.00061 0.25 6 4 2 5 3 3 2227.29774 2227.29839 -0.00065 0.25 7 4 4 6 3 3 2227.37801 2227.37803 -0.00002 1.00 7 4 3 6 3 4 2227.38185 2227.38184 0.00001 1.00 5 5 0 4 4 1 2227.42659 2227.42642 0.00016 0.25 5 5 1 4 4 0 2227.42659 2227.42642 0.00016 0.25 8 4 5 7 3 4 2227.45644 2227.45667 -0.00022 1.00
6 5 1 5 4 2 2227.50945 2227.50938 0.00007 0.25 6 5 2 5 4 1 2227.50945 2227.50936 0.00009 0.25 9 4 6 8 3 5 2227.53119 2227.53156 -0.00037 1.00 7 5 2 6 4 3 2227.59209 2227.59224 -0.00015 0.25 7 5 3 6 4 2 2227.59209 2227.59216 -0.00007 0.25 11 4 8 10 3 7 2227.66293 2227.66304 -0.00010 1.00 8 5 4 7 4 3 2227.67511 2227.67468 0.00042 0.25 8 5 3 7 4 4 2227.67511 2227.67498 0.00012 0.25 9 5 4 8 4 5 2227.75734 2227.75757 -0.00023 0.25 9 5 5 8 4 4 2227.75734 2227.75667 0.00066 0.25 7 6 2 6 5 1 2227.80253 2227.80224 0.00028 0.25 7 6 1 6 5 2 2227.80253 2227.80224 0.00028 0.25 8 6 3 7 5 2 2227.88545 2227.88521 0.00024 0.25 8 6 2 7 5 3 2227.88545 2227.88521 0.00023 0.25 11 5 7 10 4 6 2227.91733 2227.91733 -0.00000 1.00 11 5 6 10 4 7 2227.92221 2227.92276 -0.00054 1.00 9 6 4 8 5 3 2227.96819 2227.96805 0.00013 0.25 9 6 3 8 5 4 2227.96819 2227.96807 0.00011 0.25 7 7 0 6 6 1 2228.01059 2228.01067 -0.00007 0.25 7 7 1 6 6 0 2228.01059 2228.01067 -0.00007 0.25 10 6 5 9 5 4 2228.05081 2228.05071 0.00010 0.25 10 6 4 9 5 5 2228.05081 2228.05078 0.00003 0.25 ******************************************************************************
Table A-4. Observed and calculated transitions for N O-DCCCCD in the region of the fundamental band of N O (units of cm -1 ). ****************************************************************************** J' Ka' Kc' J" Ka" Kc" Observed Calculated Obs-Calc Weight ****************************************************************************** 4 4 1 5 5 0 2224.78432 2224.78432 -0.000001 0.25 4 4 0 5 5 1 2224.78432 2224.78432 -0.000004 0.25 6 3 4 7 4 3 2224.82286 2224.82278 0.000086 1.00 6 3 3 7 4 4 2224.82767 2224.82750 0.000168 1.00 4 3 2 5 4 1 2224.98345 2224.98323 0.000226 0.25 4 3 1 5 4 2 2224.98345 2224.98362 -0.000165 0.25 6 2 5 7 3 4 2224.99255 2224.99153 0.001019 1.00 7 2 5 8 3 6 2225.00849 2225.00895 -0.000466 1.00 5 2 4 6 3 3 2225.08651 2225.08668 -0.000174 1.00 4 2 3 5 3 2 2225.17501 2225.17514 -0.000130 1.00 4 2 2 5 3 3 2225.19063 2225.19080 -0.000170 1.00 8 1 7 9 2 8 2225.24995 2225.24986 0.000088 1.00 3 2 2 4 3 1 2225.25906 2225.25924 -0.000176 1.00 9 1 8 10 1 9 2225.27476 2225.27445 0.000311 1.00 8 2 6 9 2 7 2225.31020 2225.31024 -0.000041 1.00 8 3 5 9 3 6 2225.32742 2225.32718 0.000240 1.00 9 1 9 10 0 10 2225.35989 2225.35982 0.000076 1.00 7 0 7 8 1 8 2225.47724 2225.47739 -0.000153 1.00 6 2 4 7 2 5 2225.48253 2225.48282 -0.000291 1.00 7 0 7 8 0 8 2225.48845 2225.48860 -0.000154 1.00 2 1 2 3 2 1 2225.51752 2225.51763 -0.000109 1.00 8 2 7 8 3 6 2225.53152 2225.53176 -0.000245 1.00 6 0 6 7 1 7 2225.53851 2225.53832 0.000190 1.00 4 2 3 4 3 2 2225.57613 2225.57614 -0.000015 1.00 5 0 5 6 1 6 2225.59733 2225.59690 0.000436 1.00
5 2 3 5 3 2 2225.60158 2225.60148 0.000092 1.00 5 0 5 6 0 6 2225.62405 2225.62394 0.000107 1.00 5 1 5 6 1 6 2225.63543 2225.63554 -0.000115 1.00 7 2 5 7 3 4 2225.63939 2225.63941 -0.000019 1.00 4 2 2 5 2 3 2225.65825 2225.65833 -0.000080 1.00 5 1 5 6 0 6 2225.66230 2225.66259 -0.000289 1.00 4 3 2 5 3 3 2225.66735 2225.66811 -0.000761 0.25 4 3 1 5 3 2 2225.66735 2225.66704 0.000309 0.25 9 2 7 9 3 6 2225.68135 2225.68167 -0.000324 1.00 5 1 5 5 2 4 2225.68894 2225.68908 -0.000135 1.00 4 0 4 5 0 5 2225.69320 2225.69307 0.000137 1.00 4 1 4 5 1 5 2225.70667 2225.70684 -0.000166 1.00 3 0 3 4 1 4 2225.71065 2225.71080 -0.000149 1.00 4 1 4 4 2 3 2225.71914 2225.71908 0.000062 1.00 3 1 2 4 1 3 2225.73427 2225.73429 -0.000018 1.00 3 2 2 4 2 3 2225.75384 2225.75372 0.000119 1.00 2 0 2 3 1 3 2225.76973 2225.76977 -0.000043 1.00 3 1 3 4 1 4 2225.77872 2225.77882 -0.000098 1.00 5 2 4 6 1 5 2225.78407 2225.78423 -0.000157 1.00 2 1 1 2 2 0 2225.79366 2225.79341 0.000249 1.00 3 1 2 3 2 1 2225.80589 2225.80583 0.000056 1.00 6 0 6 6 1 5 2225.81229 2225.81219 0.000097 1.00 2 1 2 3 1 3 2225.85140 2225.85147 -0.000066 1.00 5 0 5 5 1 4 2225.86516 2225.86523 -0.000071 1.00 4 2 3 5 1 4 2225.89018 2225.89045 -0.000275 1.00 1 0 1 2 0 2 2225.91523 2225.91498 0.000253 1.00 2 1 2 3 0 3 2225.92010 2225.92011 -0.000016 1.00 1 1 1 2 1 2 2225.92471 2225.92469 0.000017 1.00 3 0 3 3 1 2 2225.93630 2225.93633 -0.000032 1.00 2 0 2 2 1 1 2225.95653 2225.95654 -0.000016 1.00 3 2 1 3 2 2 2226.07532 2226.07522 0.000098 1.00 2 1 1 2 1 2 2226.10629 2226.10596 0.000330 1.00
1 0 1 0 0 0 2226.15194 2226.15206 -0.000124 1.00 1 1 0 1 0 1 2226.17603 2226.17604 -0.000003 1.00 2 1 1 2 0 2 2226.18823 2226.18826 -0.000027 1.00 3 1 2 3 0 3 2226.20835 2226.20832 0.000028 1.00 4 1 3 4 0 4 2226.23804 2226.23797 0.000074 1.00 5 1 4 5 0 5 2226.27812 2226.27875 -0.000629 1.00 3 1 3 2 1 2 2226.29250 2226.29247 0.000031 1.00 3 0 3 2 0 2 2226.30724 2226.30676 0.000478 1.00 6 1 5 6 0 6 2226.33153 2226.33120 0.000325 1.00 3 2 1 3 1 2 2226.33670 2226.33672 -0.000021 1.00 8 2 6 8 1 7 2226.34560 2226.34523 0.000370 1.00 6 1 5 5 2 4 2226.35736 2226.35769 -0.000338 1.00 4 1 4 3 1 3 2226.36475 2226.36479 -0.000032 1.00 4 1 3 3 1 2 2226.40981 2226.40991 -0.000098 1.00 8 3 5 8 2 6 2226.47608 2226.47642 -0.000340 1.00 7 3 4 7 2 5 2226.49869 2226.49871 -0.000018 1.00 6 1 6 5 1 5 2226.50694 2226.50701 -0.000065 1.00 2 2 0 1 1 1 2226.53036 2226.53044 -0.000072 1.00 5 3 2 5 2 3 2226.53684 2226.53658 0.000257 1.00 6 2 5 5 2 4 2226.54262 2226.54168 0.000944 1.00 3 3 0 3 2 1 2226.55491 2226.55460 0.000309 1.00 5 3 3 5 2 4 2226.56673 2226.56665 0.000071 1.00 7 1 7 6 1 6 2226.57657 2226.57692 -0.000354 1.00 3 2 2 2 1 1 2226.58646 2226.58620 0.000258 0.25 7 0 7 6 0 6 2226.58646 2226.58658 -0.000121 0.25 7 1 7 6 0 6 2226.60362 2226.60396 -0.000343 1.00 7 2 6 6 2 5 2226.61777 2226.61767 0.000105 1.00 3 2 1 2 1 2 2226.62477 2226.62484 -0.000070 1.00 8 0 8 7 1 7 2226.63516 2226.63520 -0.000044 1.00 7 2 5 6 2 4 2226.65815 2226.65829 -0.000134 1.00 8 1 8 7 0 7 2226.66395 2226.66390 0.000049 1.00 9 1 8 8 2 7 2226.67326 2226.67344 -0.000181 1.00
8 2 7 7 2 6 2226.69252 2226.69257 -0.000043 1.00 9 0 9 8 1 8 2226.70805 2226.70811 -0.000053 1.00 9 1 9 8 1 8 2226.71462 2226.71479 -0.000171 1.00 7 4 3 7 3 4 2226.73713 2226.73761 -0.000483 1.00 6 2 5 5 1 4 2226.75643 2226.75648 -0.000049 1.00 9 2 8 8 2 7 2226.76645 2226.76631 0.000138 1.00 10 0 10 9 1 9 2226.77921 2226.77900 0.000213 1.00 3 3 0 2 2 1 2226.79695 2226.79744 -0.000485 0.25 3 3 1 2 2 0 2226.79695 2226.79642 0.000534 0.25 7 2 6 6 1 5 2226.80360 2226.80356 0.000040 1.00 4 3 2 3 2 1 2226.87373 2226.87365 0.000080 1.00 4 3 1 3 2 2 2226.87874 2226.87881 -0.000070 1.00 5 3 2 4 2 3 2226.96279 2226.96273 0.000060 1.00 4 4 0 3 3 1 2227.06853 2227.06896 -0.000426 0.25 4 4 1 3 3 0 2227.06853 2227.06890 -0.000371 0.25 7 3 5 6 2 4 2227.07595 2227.07580 0.000152 1.00 5 4 2 4 3 1 2227.14806 2227.14820 -0.000140 0.25 5 4 1 4 3 2 2227.14806 2227.14858 -0.000525 0.25 6 4 2 5 3 3 2227.22764 2227.22836 -0.000718 0.25 6 4 3 5 3 2 2227.22764 2227.22681 0.000830 0.25 7 4 3 6 3 4 2227.30857 2227.30860 -0.000030 1.00 5 5 1 4 4 0 2227.34004 2227.34009 -0.000058 1.00 5 5 0 4 4 1 2227.34004 2227.34010 -0.000061 1.00 8 4 5 7 3 4 2227.37881 2227.37840 0.000410 1.00 8 4 4 7 3 5 2227.38984 2227.38995 -0.000111 1.00 6 5 2 5 4 1 2227.41948 2227.41958 -0.000104 0.25 6 5 1 5 4 2 2227.41948 2227.41960 -0.000126 0.25 9 4 6 8 3 5 2227.44869 2227.44848 0.000209 1.00 7 5 2 6 4 3 2227.49894 2227.49900 -0.000060 0.25 7 5 3 6 4 2 2227.49894 2227.49889 0.000050 0.25 8 5 3 7 4 4 2227.57826 2227.57826 -0.000004 0.25 8 5 4 7 4 3 2227.57826 2227.57786 0.000401 0.258 2 7 7 2 6 2226.69252 2226.69257 -0.000043 1.00 9 0 9 8 1 8 2226.70805 2226.70811 -0.000053 1.00 9 1 9 8 1 8 2226.71462 2226.71479 -0.000171 1.00 7 4 3 7 3 4 2226.73713 2226.73761 -0.000483 1.00 6 2 5 5 1 4 2226.75643 2226.75648 -0.000049 1.00 9 2 8 8 2 7 2226.76645 2226.76631 0.000138 1.00 10 0 10 9 1 9 2226.77921 2226.77900 0.000213 1.00 3 3 0 2 2 1 2226.79695 2226.79744 -0.000485 0.25 3 3 1 2 2 0 2226.79695 2226.79642 0.000534 0.25 7 2 6 6 1 5 2226.80360 2226.80356 0.000040 1.00 4 3 2 3 2 1 2226.87373 2226.87365 0.000080 1.00 4 3 1 3 2 2 2226.87874 2226.87881 -0.000070 1.00 5 3 2 4 2 3 2226.96279 2226.96273 0.000060 1.00 4 4 0 3 3 1 2227.06853 2227.06896 -0.000426 0.25 4 4 1 3 3 0 2227.06853 2227.06890 -0.000371 0.25 7 3 5 6 2 4 2227.07595 2227.07580 0.000152 1.00 5 4 2 4 3 1 2227.14806 2227.14820 -0.000140 0.25 5 4 1 4 3 2 2227.14806 2227.14858 -0.000525 0.25 6 4 2 5 3 3 2227.22764 2227.22836 -0.000718 0.25 6 4 3 5 3 2 2227.22764 2227.22681 0.000830 0.25 7 4 3 6 3 4 2227.30857 2227.30860 -0.000030 1.00 5 5 1 4 4 0 2227.34004 2227.34009 -0.000058 1.00 5 5 0 4 4 1 2227.34004 2227.34010 -0.000061 1.00 8 4 5 7 3 4 2227.37881 2227.37840 0.000410 1.00 8 4 4 7 3 5 2227.38984 2227.38995 -0.000111 1.00 6 5 2 5 4 1 2227.41948 2227.41958 -0.000104 0.25 6 5 1 5 4 2 2227.41948 2227.41960 -0.000126 0.25 9 4 6 8 3 5 2227.44869 2227.44848 0.000209 1.00 7 5 2 6 4 3 2227.49894 2227.49900 -0.000060 0.25 7 5 3 6 4 2 2227.49894 2227.49889 0.000050 0.25 8 5 3 7 4 4 2227.57826 2227.57826 -0.000004 0.25 8 5 4 7 4 3 2227.57826 2227.57786 0.000401 0.25