M. I. El Idrissi

Vibrational Spectroscopic Database on Acetylene, X̃ 1Σg+(12C2H2,12C2D2, and 13C2H2)

Information on the vibrational energy states in acetylene (12C2H2, 12C2D2, and 13C2H2) is gathered: spectroscopic constants (vibrational frequencies and anharmonicities, vibration-rotation interaction parameters), observed vibrational energy states and complete sets of predicted vibrational energies and predicted principal rotational constants Bv for states of 12C2H2, 12C2D2, and 13C2H2 up to 15000, 10000, and 12000 cm−1, respectively. Statistical parameters (partition functions and integrated number of states) deduced from these predicted spectroscopic data are provided for the three isotopomers. The equilibrium geometrical structure is determined to be re(CH)=106.138(35) pm and re(CC)=120.292(13) pm from constants available for 12C2H2, 12C2D2, 13C2H2, and 12C2HD.

The Vibrational Energy Pattern in Acetylene (IV): Updated Global Vibration Constants for 12C2H2

All 253 vibrational levels in the ground electronic state of 12C2H2 with assigned rotational structure reported in the literature from absorption, stimulated emission pumping, and dispersed laser induced fluorescence spectroscopic investigations are gathered. They cover the range up to 18 915 cm−1. Some 219 of these energies are simultaneously fitted using the same so-called Cluster model based on the emergence of three constants of the motion, as previously used to deal with the vibrational energy levels up to 12 000 cm−1 [Abbouti Temsamani and Herman, J. Chem. Phys. 103, 5931 (1995)]. Thirty-nine vibrational constants are produced. The rms value of the fit is 0.81 cm−1. Principal rotational constants are predicted for all levels, which satisfactorily compare with the experimental results. Problems are demonstrated to concern a fraction of the 34 remaining levels only. Thus, the adequacy of the model is fully confirmed. The remaining problems are discussed and globally attributed to problems of a vibrati...

The vibrational energy levels in acetylene. III. 12C2D2

We have performed the rovibrational analysis of the absorption spectrum of 12C2D2 between 5150 and 8000 cm−1, recorded by Fourier transform absorption spectroscopy, and between 12 800 and 16 600 cm−1, recorded by intracavity laser absorption spectroscopy. Respectively 10 and 9 bands are reported for the first time in each range. Improved or new rovibrational parameters were obtained for 34 vibrational levels altogether. The vibrational energies we obtained, together with those reported in the literature, were taken into account to model the vibrational energy pattern in 12C2D2(X 1Σg+). The analysis was performed in successive steps, inferring each time suitable parameters. The 44/55, 11/33, 12/33, and 1/244 quartic order anharmonic resonances were introduced during the procedure. They altogether define vibrational clusters which are characterized by only two dynamical constants of motion, Ns=V1+V2+V3 and k=l4+l5.

The vibrational energy pattern in acetylene. V. 13C2H2

A total of 134 vibrational levels with assigned rotational structure have been gathered in the ground electronic state of 13C2H2. Most of these measurements are updated or new compared to the previously published data. Altogether, they cover the range up to 23 670 cm−1. 118 out of the 119 levels observed below 13 000 cm−1 have been simultaneously fitted using the so-called cluster model, already used to deal with the vibrational energy levels in other isotopomers of acetylene [El Idrissi et al., J. Chem. Phys. 110, 2074 (1999), and references therein]. Twenty-nine vibrational constants have been determined, including the off-diagonal parameters K3/245, K1/244, K1/255, K11/33, K14/35, and r45, with a rms of the fit equal to 0.52 cm−1. The same three constants of the motion as in 12C2H2 emerged, Ns=v1+v2+v3, Nr=5v1+3v2+5v3+v4+v5 and k=l4+l5. The energies of the levels above 13 000 cm−1 calculated with the obtained parameters compare reasonably well with the experimental values. For all levels the predicted ...

The vibrational energy pattern in acetylene (VI): Inter- and intrapolyad structures

Intra- and interpolyad structures are investigated in the vibrational energy pattern of acetylene, using the spectroscopic Hamiltonian presented in previous papers in this series [see El Idrissi et al., J. Chem. Phys. 110, 2074 (1999)]. The existence of two constants of the motion is shown to generate very regular patterns in the manifold of vibrational energy levels. Distinct regular and oscillatory contributions are evidenced in the number of vibrational levels in the main polyads, which are fully reproduced using the generating function presented in Sadovskii and Zhilinskii [J. Chem. Phys. 103, 10520 (1995)]. Further developments of this approach are outlined.

The integrated number of vibrational states in acetylene (12C2H2, 13C2H2, 12C2D2)

A calculated exhaustive set of vibrational state energies in 12C2H2, 13C2H2 and 12C2D2 has been used to analyse the evolution of the integrated number of states with increasing vibrational energy N(E) up to 15000 cm−1, 12000cm−1 and 10000 cm−1 in each isotopomer, respectively. The regular contribution to N(E) was modelled analytically and numerical parameters were fitted. The other expected contribution to N(E), which is of oscillatory nature, was quantified and is discussed using energyand time-dependent theories. Related periods of oscillation and temporal recurrences are interpreted consistently in terms of the constant of the motion Nr = 5v2 + 3v2 + 5v3 + v4 + v5 and of an average vibrational quantum. More pragmatically, the vibrational dynamics appear to be dominated by the bending vibrations, i.e., by the slowest oscillators.

The absorption spectrum of 12C2H2 IV. The regions 7600–9200 cm−1 and 10600–11500 cm−1

The absorption spectrum of 12C2H2 has been recorded by intracavity laser absorption spectroscopy (ICLAS) in the 10600–11 500 cm−1 spectral region, where no absorption bands were previously reported. Fifteen bands starting from the vibrational ground state are observed and rotationally analysed. All corresponding excited vibrational levels were assigned using the polyad model, the so-called cluster model (El Idrissi, M.I., Liévin, J., Campargue, A., and Herman, M., 1999, J. chem. Phys., 110, 2074) which allows vibrational energies, rotational Bv constants and, to some respect, relative band intensities to be predicted. Additional data and constants are also provided in the range 7600–9200cm−1, whenever improving the literature results, from spectra recorded previously at ULB using Fourier transform spectroscopy. The assignment procedure in the range recorded by ICLAS is detailed, leading to a deeper understanding of vibration-rotation and intensity features of the absorption bands within the frame of the cluster model.

The absorption spectrum of 12C2D2 in the 10000-12500 cm–1 spectral region

The absorption spectrum of dideuteroacetylene has been recorded by intracavity laser absorption spectroscopy (ICLAS) in the 10 200–12 500cm−1 spectral region. Among 25 absorption bands of 12C2D2 rotationally analysed in this spectral region, 17 are newly observed. They include one IIu-Σ+ g and thirteen Σ+ u-Σ+ g bands starting from the vibrational ground state and eleven hot bands from the V 4 = 1 and V 5 = 1 lower states. The rotational structure of two excited levels is affected by a strongly J-dependent interaction with a perturber which induces intensity transfer to extra lines. The coupling is identified as a I-resonance interaction with δu dark states and the vibrational assignment of the perturbers is discussed. Two Σ-Σ bands of the 12C13 CD2 species, present in natural abundance in the sample, could also be identified and rotationally analysed. Most of the corresponding excited vibrational levels of 12C2D2 were unambiguously assigned using the polyad model [Herman, M., el idrissi, M. I., Pisarchik, A., Campargue, A., Gaillot, A.-C., Biennier, L., di lonardo, G. and Fusina, L., 1998, J. chem. Phys., 108, 1377] which allows vibrational energies and B V rotational constants to be predicted. In particular the previously highlighted 1/244 anharmonic resonance is confirmed by energy and intensity features in several {(V 1, V 2, V 3, V 4 = 0, V 5 = 0),(V 1 −1, V 2 + 1, V 3 V 4 = 2, V 5 = 0)} dyads. Significant deviations between predicted and experimental energy levels are observed for a few levels and discussed.