Ab Initio Potential Energy Curves for the Ground and Low Lying Excited States of NH- and the Effect of 2 Sigma(+/-) States on A-Doubling of the Ground State X-2 pi

作者：Srivastava Saurabh; Sathyamurthy N^*

来源：Journal of Physical Chemistry A, 2013, 117(36): 8623-8631.

DOI：10.1021/jp4027628

Complete basis set extrapolated ab initio potential energy curves obtained from multireference configuration interaction (MRCI) level calculations for the ground state (x(2)n) and the a(4)Sigma(-) state of NH and the ground state (X-3 Sigma(-)) of NH are reported. The potential energy curves for the A%26apos;(2)Sigma(-) and A(2)Sigma(-) states of NH- have been computed using the V6Z basis set at the MRCI level. A-doubling parameters p and q are calculated for the ground and the first excited vibrational states of the ground electronic state of NH-, using second-orderperturbation theory. The effect of the 2 Sigma(+) and (2)Sigma(-) states on the A-doubling values is discussed. Earlier experiments had not considered the influence of the 2 Sigma(-) state on p and q while fitting the spectral data. Using the computed potential energy curves and the ro-vibrational spectra including the fine splitting, we have computed the threshold for electron detachment. The result is in agreement with the experimental values of Neumark et al. [J. Chem. Phys. 1985, 83, 4364] and Farley et al. [Phys. Rev. A 1987, 35, 1099].

• 出版日期2013-9-12