ABSTRACT
As one of the most important diatomic molecules in the universe, the spectroscopic characterizations of C2 have attracted wide attention in various fields, such as interstellar chemistry, planetary atmospheric chemistry, and combustion. In recent years, a systematic spectroscopic study of C2 in the vacuum ultraviolet (VUV) region has been carried out in our laboratory by using the (1VUV+1'UV) resonance-enhanced multiphoton ionization method based on the combination of a tunable VUV laser source and a time-of-flight mass spectrometer. Two new electronic transition band systems have been reported, following the pioneering work of Herzberg and co-workers in 1969. In the current study, a total of 18 vibronic transition bands of C2 from the lower a3Πu state are experimentally observed in the VUV photon energy range 72000-81000 cm-1, and 6 new upper vibronic levels of 3Δg symmetry are identified, which are assigned as the v' = 0-5 vibrational levels of the 33Δg state of C2. The term energy Te of the 33Δg state is determined to be in the range of 78425-78475 cm-1 (9.724-9.730 eV) with respect to the ground X1Σg+ state, and the molecular constants such as vibrational and rotational constants are also determined, which are in reasonable agreement with those predicted by high-level ab initio theoretical calculations. Irregular vibrational energy level spacings in the 33Δg state are observed, which is tentatively attributed to the strong perturbations between the 33Δg and 23Δg states, as previously predicted by theory.
ABSTRACT
A systematic spectroscopic study of the dicarbon molecule C2 has important applications in various research fields, such as astrochemistry and combustion. In the short vacuum ultraviolet (VUV) wavelength region, recent theoretical calculations have predicted many absorption band systems of C2, but only few of them have been verified experimentally yet. In this work, we employed a tunable VUV laser radiation source based on the two-photon resonance-enhanced four-wave mixing method and a time-of-flight mass spectrometer to investigate the absorption bands of C2 in the VUV range of 64 000-66 000 cm-1. The electronic transition 23Σg-(v')-a3Πu(vâ³) of C2 has been observed and identified experimentally for the first time. The term value Te for the 23Σg- state is determined to be 66 389.9 ± 0.5 cm-1 above the ground state X1Σg+, and the vibrational and rotational constants are also determined. The experimentally measured spectroscopic parameters in this study are in excellent agreement with the theoretical results based on high-level ab initio calculations.
ABSTRACT
The dicarbon radical, C2, is one of the most abundant molecules in the universe, and has been widely observed in various energetic environments. Even though numerous experimental and theoretical investigations on C2 have been done during the last two centuries, spectroscopic study of C2 in vacuum ultraviolet (VUV) region has been rare. The only three known absorption band systems in VUV region were identified by Herzberg and co-workers in 1969 by VUV spectrograph, namely the electronic transitions F1Πu(v')-X1Σg +(vâ³), f3Σg -(v')-a3Πu(vâ³) and g3Δg(v')-a3Πu(vâ³) (Herzberg-Lagerqvist-Malmberg transitions). In this study, we employ a two-photon resonance-enhanced four-wave mixing based VUV laser source and a time-of-flight mass spectrometer for reinvestigating the above three electronic transitions of C2 through a resonant (1VUV + 1'UV) photoionization scheme. Besides those vibronic transitions as identified by Herzberg and co-workers, many more absorption bands belonging to the electronic transitions f3Σg -(v')-a3Πu(vâ³) and g3Δg(v')-a3Πu(vâ³) are observed with their spectroscopic parameters determined. The rather astrophysically important F1Πu state is not observed here by the resonant (1VUV + 1'UV) photoionization scheme, which must be due to its fast predissociation process. Instead, our study shows that the vibronic band g3Δg(v' = 2)-a3Πu(vâ³ = 0) exactly overlaps with F1Πu(v' = 0)-X1Σg +(vâ³ = 0), which was not realized in previous studies. The potential implications of these findings to astronomical observations are discussed.
ABSTRACT
As one of the most abundant molecules in the universe, the long history of spectroscopic studies of the dicarbon molecule, C2, reaches back two centuries. While many electronic band systems with upper states below the lowest dissociation threshold have been well characterized, much less is known about transitions to higher-lying states. Here, we report the observation of a new band system of C2 from the lowest triplet state a3Πu through a resonance-enhanced multiphoton ionization scheme. The upper state is identified as 13Σg+, which is determined to be 61539.0 cm-1 (7.630 eV) above ground state X1Σg+. The spectroscopic parameters determined for the 13Σg+ state are in excellent agreement with those predicted by the high-level ab initio calculations. This study paves the way for systematic investigations of the photoabsorption and photodissociation of C2 in the vacuum ultraviolet region, which has important applications in the field of astrochemistry.
ABSTRACT
The C+ ion photofragment spectra and photodissociation branching ratios into the two energetically available channels, C(1D) + O(3P) and C(3P) + O(3P), have been obtained for the three CO isotopologues, 12C16O, 13C16O, and 12C18O, in the vacuum ultraviolet range 100500-102320 cm-1. The two vibronic states of 1Σ+ symmetry, F(3dσ) 1Σ+(υ' = 1) and J(4sσ) 1Σ+(υ' = 0), predominantly dissociate into the lowest channel C(3P) + O(3P) through interactions with the repulsive D'1Σ+ state. All three vibronic states of 1Π symmetry, E'1Π(υ' = 1, 2) and G(3dπ) 1Π(υ' = 0), dissociate into both of the channels above. The photodissociation branching ratios into the channel C(1D) + O(3P) for E'1Π(υ' = 1, 2) are found to be independent of both the rotational quantum number and e/f parity, while those for G(3dπ) 1Π(υ' = 0) strongly depend on the rotational quantum number, indicating very different predissociation pathways between the valence states E'1Π(υ' = 1, 2) and the Rydberg state G(3dπ) 1Π(υ' = 0). The potential energy curves of CO in the aforementioned energy range and below have recently been well constructed due to a series of interplays between high-resolution spectroscopic studies and theoretical calculations; the photodissociation branching ratios measured in this study can provide further benchmarks for future theoretical investigations which aim to understand the detailed predissociation dynamics of CO.
ABSTRACT
A recent high resolution photoabsorption study revealed that the Rydberg W1Π(ν = 1) level of carbon monoxide (CO) is perturbed by the valence Eâ³1Π(ν = 0) level, and the predissociation linewidth shows drastic variation at the crossing point due to the interference effect [Heays et al., J. Chem. Phys. 141(14), 144311 (2014)]. Here, we reinvestigate the Rydberg W1Π(ν = 1) level for the three CO isotopologues, 12C16O, 13C16O, and 12C18O, by measuring the rotationally dependent photodissociation branching ratios. The C+ ion photofragment spectra obtained here reproduce the recent high resolution photoabsorption spectra very well, including the presence of the valence Eâ³1Π(ν = 0) level. The photodissociation branching ratios into the spin-forbidden channel C(1D) + O(3P) show sudden increases at the crossing point between the W1Π(ν = 1) and Eâ³1Π(ν = 0) levels, which is in perfect accordance with the drastic variation of the linewidth observed in the recent spectroscopic study. Further analysis reveals that the partial predissociation rate into the lowest channel C(3P) + O(3P) shows a much more prominent decrease at the crossing point, which is caused by the interference effect between the W1Π(ν = 1) and Eâ³1Π(ν = 0) levels, than that into the spin-forbidden channel C(1D) + O(3P), and this is the reason of the sudden increase as observed in the photodissociation branching ratio measurements. We hope that the current experimental investigation will stimulate further theoretical studies, which could thoroughly address all the experimental observations in a quantitative way.
