High-resolution infrared spectroscopy of trans- and cis-H(18)ON(18)O: equilibrium structures of the nitrous acid isomers

In this paper, we present the first high-resolution spectra and analysis of the nu 4 fundamental bands of fully (18)O-substituted nitrous acid, trans- and cis-H(18)ON(18)O. These bands are not perturbed by neighboring vibrational levels and were used to determine for the first time accurate rotational and centrifugal distortion constants of the ground and nu 4 = 1 states of trans- and cis-H(18)ON(18)O. The ground-state rotational constants were then used, together with the rotational constants of other HONO isotopic species and with rotation-vibration parameters from ab initio calculations, to determine accurate semi-experimental equilibrium structures of trans- and cis-HONO. Our study confirms the results of a recent work by Demaison et al. (J. Phys. Chem. A 2006, 110, 13609-13617) concerning the structure of trans-HONO, whereas the new structure of cis-HONO obtained in this paper is a significant improvement compared with the previous work of Cox et al. (J. Mol. Struct. 1994, 320, 91-106). The recommended parameters for the equilibrium structure of cis-HONO are r(e)(ON) = 1.1816(10) A, r(e)(N-O) = 1.3887(10) A, r(e)(O-H) = 0.9744(7) A, angle(e)(ONO) = 113.18(1) degrees, and angle(e)(HON) = 104.67(4) degrees.