Vibration-rotation pattern in acetylene. II. Introduction of Coriolis coupling in the global model and analysis of emission spectra of hot acetylene around 3 μm

Abstract

A high temperature source has been developed and coupled to a high resolution Fourier transform spectrometer to record emission spectra of acetylene around 3 mum up to 1455 K under Doppler limited resolution (0.015 cm(-1)). The nu(3)-ground state (GS) and nu(2)+nu(4)+nu(5) (Sigma(u) (+) and Delta(u))-GS bands and 76 related hot bands, counting e and f parities separately, are assigned using semiautomatic methods based on a global model to reproduce all related vibration-rotation states. Significantly higher J-values than previously reported are observed for 40 known substates while 37 new e or f vibrational substates, up to about 6000 cm(-1), are identified and characterized by vibration-rotation parameters. The 3 811 new or improved data resulting from the analysis are merged into the database presented by Robert et al. [Mol. Phys. 106, 2581 (2008)], now including 15 562 lines accessing vibrational states up to 8600 cm(-1). A global model, updated as compared to the one in the previous paper, allows all lines in the database to be simultaneously fitted, successfully. The updates are discussed taking into account, in particular, the systematic inclusion of Coriolis interaction.

A test of optimal laser impulsion for controlling population within theNs = 1,Nr = 5 polyad of12C2H2

“…The version selected here [9] reproduces all 15,562 data published at the time within three times their experimental measurement precision. This precision was typically between 10 -4 and 10 -3 cm -1 .…”

“…$! focus on acetylene ( 12 C2H2), taking advantage of the existence in the literature of a global Hamiltonian describing its vibrational and rotational energy levels within experimental precision, up to the near-infrared spectral range [9,10]. The transition dipole moments, which are essential for the optimal control, have also been extracted from the experimental data.…”

A four-atom molecule at the forefront of spectroscopy, intramolecular dynamics and astrochemistry: Acetylene

“…Inclusion of Coriolis vibration-rotation interaction was later made possible, systematically [30], leading to a merge of those polyads with different N s but identical N r values in the block-Hamiltonian. Thanks to the development of the global Fig.…”

Vibration–rotation alchemy in acetylene (12C2H2), at low vibrational excitation: from high resolution spectroscopy to fast intramolecular dynamics

“…All of the interactions are well characterized spectroscopically 43 . The contribution of the bright zeroth-order substate to the selected 10 relevant eigenstates, labeled I to X, is shown in Figure 7b.…”

“…Recently, a detailed global model has been reported which simultaneously treats both the vibrational and rotational structure in 38,39 Deleted: 40 Deleted: 19…40,41 Deleted: 43 ... [37] ... [36] ... [27] ... [22] ... [28] ... [26] ... [40] ... [29] ... [24] ... [30] ... [41] ... [35] ... [42] ... [31] ... [38] ... [43] ... [32] ... [39] ... [44] ... [33] ... [45] ... [34] ... [46] ... [23] ... [47] ... [25] F o r P e e r R e v i e w O n l y 7 The reliability and global nature of this spectroscopic Hamiltonian may shed some new light on the vibrational and also rotational aspects of IVR.…”