THE JAHN-TELLER (JT) EFFECT IN THE $\widetilde{A}$ STATE OF THE NITRATE RADICAL NO$_3$
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Date
2009
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Publisher
Ohio State University
Abstract
The JT effect in the $\widetilde{A}$$^2$E$^{\prime \prime}$ of NO$_3$ is poorly understood. A preliminary spectrum of the vibronically-allowed $\widetilde{A}$$\leftarrow$$\widetilde{X}$ transition, coupled with ab initio calculations, shows moderate JT activity in the $\widetilde{A}$ state. Vibronic bands exhibit either static or dynamic JT distortions depending on the vibrational level of the upper $\widetilde{A}$ state. The picture of the $\widetilde{A}$ state is however incomplete. For example, in the E$^{\prime \prime}$$\otimes$e$^{\prime}$=a$_1$$^{\prime \prime}$$\oplus$a$_2$$^{\prime \prime}$$\oplus$e$^{\prime \prime}$ manifold, while the splitting would provide a direct measure of the JT strength, only the a$_1$$^{\prime \prime}$ levels have been observed. We have gained new insight into the $\widetilde{A}$ state by examining the hot bands of NO$_3$ which access previously unobserved dark levels of the $\widetilde{A}$ state.
Description
Author Institution: Arthur Amos Noyes Laboratory of Chemical Physics, California Institute of Technology, Pasadena, California 91125; Department of Chemistry, University of Texas at Austin, Austin, TX 78712