Document Type

Article

Publication Date

2-2015

DOI

10.1063/1.4907530

Publication Title

Journal of Chemical Physics

Volume

142

Issue

6

Pages

064317 (1-11)

Abstract

6229 lines of the Ballik-Ramsay system (b3Σg--a3Πu) and the Phillips system (A1Πu-X1Σg+) of C2 up to v = 8 and J = 76, which were taken from the literature or assigned in the present work, were analyzed simultaneously by least-squares fitting with 82 Dunham-like molecular parameters and spin-orbit interaction constants between the b3Σg- and X1Σg+ states with a standard deviation of 0.0037 cm-1 for the whole data set. As a result of the deperturbation analysis, the spin-orbit interaction constant AbX was determined as 6.333(7) cm-1 and the energy difference between the X1Σg+ and a3Πu states was determined as 720.008(2) cm1 for the potential minima or 613.650(3) cm-1 for the v = 0 levels with Merer and Brown's N2 Hamiltonian for 3Π states, which is about 3.3 cm-1 larger than the previously determined value. Due to this sizable change, a new energy-level crossing was found at J = 2 for v = 3 (F1) of b3Σg- state and v = 6 of X1Σg+ state, where the strong interaction causes a nearly complete mixing of the wave functions of the b3Σg- and X1Σg+ states and the forbidden transitions become observable. Using the predictions of our deperturbation analysis, we were able to identify 16 forbidden transitions between the singlet and triplet states at the predicted frequencies with the expected intensities, which verifies our value for the energy difference between the X1Σg+ and a3Πu states. © 2015 AIP Publishing LLC.

Original Publication Citation

Chen, W., Kawaguchi, K., Bernath, P. F., & Tang, J. (2015). Simultaneous analysis of the Ballik-Ramsay and Phillips systems of C2 and observation of forbidden transitions between singlet and triplet states. Journal of Chemical Physics, 142(6). doi:10.1063/1.4907530

ORCID

0000-0002-1255-396X (Bernath)

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