Abstract
The protocol MARVEL, standing for measured active rotational–vibrational energy levels, is used to study high-accuracy measurements of rotational lines of four isotopologues of water, H 2 16 O , H 2 17 O , H 2 18 O , and D 2 16 O , obtained by spectroscopy in the far-infrared (FIR) region of 15–170 cm −1 by Matsushima et al. [Matsushima F, Odashima H, Iwasaki T, Tsunekawa S, Takagi K. Frequency measurement of pure rotational transitions of H 2O from 0.5 to 5 THz. J Mol Struct 1995; 352/353, 371–8; Matsushima F, Nagase H, Nakauchi T, Odashima H, Takagi K. Frequency measurement of pure rotational transitions of H 2 17 O and H 2 18 O from 0.5 to 5 THz. J Mol Spectrosc 1999;193: 217–23; Matsushima F, Matsunaga M, Qian GY, Ohtaki Y, Wang RL, Takagi K. Frequency measurement of pure rotational transitions of D 2O from 0.5 to 5 THz. J Mol Spectrosc 2001;206: 41–6; Matsushima F, Tomatsu N, Nagai T, Moriwaki Y, Takagi K. Frequency measurement of pure rotational transitions in the v 2=1 state of H 2O. J Mol Spectrosc 2006;235: 190–5]. MARVEL validates the high accuracy of most of the measured line positions. It results in a considerable number of energy levels with an average internal uncertainty of only 40 kHz (2 σ). It also supports serious inaccuracy problems when Watson-type A-reduced Hamiltonians are used for predicting the highly accurate rotational measurements for water. Finally, MARVEL suggests a large number of para-water levels, for example 41 for H 2 16 O , which are candidates for becoming frequency standards in the FIR region of 15–170 cm −1 (the 0.5–5 THz window) when an accuracy of about 0.1 MHz is deemed to be sufficient.
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More From: Journal of Quantitative Spectroscopy and Radiative Transfer
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