Rotational analysis of bands of the (A)over-tilde - (X)over-tilde transition of the C3Ar van der Waals complex

摘要

Rotational analyses have been carried out for four of the strongest bands of the (A) over tilde - (X) over tilde 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 (A) over tilde (1)Pi(u)-(x) over bar (1)Sigma(+)(g) transition of C-3 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)Pi(u)vibronic state of C-3, 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 3.75(5) angstrom, 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 C-3 unit is non-linear, and that the complex does not have a rigid-molecule structure, existing instead as a superposition of arrowhead (up arrow) and distorted Y-shaped (Y) structures. (C) 2015 AIP Publishing LLC.