AB INITIO CALCULATIONS OF THE LOW LYING $^2\Pi$ STATES OF NO
Loading...
Date
2006
Authors
Schwenke, David W.
Journal Title
Journal ISSN
Volume Title
Publisher
Ohio State University
Abstract
The NO molecule has too many electrons. The ground electronic state is of $^2\Pi$ symmetry, and can only form a double bond. The valence electronically excited $^2\Pi$ states are many, and can only form single bonds or are repulsive. In contrast, the NO$^+$ molecule can form a triple bond. Thus there are strongly bound Rydberg states in NO, and these give rise to a myriad of avoided crossings in the Born-Oppenheimer (BO) picture. These crossings are very troublesome, for example the B,C avoided crossing occurs at $v=3$ for the C state, and this causes vibrational calculations using the BO picture to be impossible. In this work we show how the BO picture can be de-perturbed in {\it ab initio} calculations without resorting to a diabatic transformation starting from the asymptotic region.
Description
Author Institution: NASA Ames Research Center, Moffett Field, CA 94035-1000