Rotational analysis of bands of the Ã - X̃ transition of the C3Ar van der Waals complex

• Published in: The Journal of chemical physics 2015-11, Vol.143 (19), p.194304-194304
• Main Authors: Merer, Anthony J, Hsu, Yen-Chu, Chen, Yi-Ren, Wang, Yi-Jen
• Format: Article
• Language: English
• Subjects: Axes of rotation; C band; Coriolis force; Coupling; Electron states; Molecular structure; Organic chemistry; Physics; Quantum chemistry; Superposition (mathematics); T shape; Time dependence
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/1.4935368

Rotational analyses have been carried out for four of the strongest bands of the Ã-X̃ transition of the C3Ar van der Waals complex, at 393 and 399 nm. These bands lie near the 02(-)0-000 and 04(-)0-000 bands of the Ã(1)Πu-X̃(1)Σ(+) g transition of C3 and form two close pairs, each consisting of a type A and a type C band of an asymmetric top, about 4 cm(-1) apart. Only K″ = even lines are found, showing that the complex has two equivalent carbon atoms (I = 0), and must be T-shaped, or nearly so. Strong a- and b-axis electronic-rotational (Coriolis) coupling occurs between the upper states of a pair, since they correlate with a (1)Πu vibronic state of C3, where the degeneracy is lifted in the lower symmetry of the complex. Least squares rotational fits, including the coupling, have given the rotational constants for both electronic states: the van der Waals bond lengths are 3.81 and 3.755 Å, respectively, in the ground and excited electronic states. For the ground state our new quantum chemical calculations, using the Multi-Channel Time-Dependent Hartree method, indicate that the C3 unit is non-linear, and that the complex does not have a rigid-molecule structure, existing instead as a superposition of arrowhead (↑) and distorted Y-shaped (Y) structures.