Analysis of the calculated X-X ro-vibrational transition intensities in molecular hydrogen

TL;DR

This study analyzes calculated X-X ro-vibrational transition intensities in molecular hydrogen, assessing the impact of different quadrupole-moment functions and identifying anomalies related to destructive interference in spectral data.

Contribution

It provides a detailed analysis of how analytic quadrupole-moment functions affect intensity calculations and identifies anomalies in line lists, enhancing understanding of molecular hydrogen spectra.

Findings

Spline interpolation does not impair intensity accuracy.

Numerous anomalies due to destructive interference are identified.

Intensities are sensitive to molecular function forms and fundamental constants.

Abstract

The potential-energy and quadrupole-moment functions of the H$_2$ ground electronic state are well known in literature (Komasa et al., 2019; Wolniewicz et al., 1998), and the line list of the vibrational-rotational transitions was calculated (Roueff et al., 2019). In this paper, we analyze the calculated intensities in order to learn how the intensities will change when analytic quadrupole-moment functions fitted to the ab initio and experimental data are used instead of spline-interpolated functions. We found that the use of splines does not deteriorate the intensities and does not lead to nonphysical saturation, as in heavier molecules, owing to the high precision of the ab initio data and the high density of the grid. The accuracy of the calculated intensities is estimated up to high overtones. Extraction of new spectroscopic information from the observational data that supplements the laboratory measurements is performed. The laboratory and observational data do not help increase the quality of the analytic functions. Numerous anomalies resulting from the destructive interference are identified in the calculated line lists, some of them being situated within the recently observed spectral regions, 1.5-2.5 $\mu$m. The intensities of these anomalies can be sensitive to the form of the molecular functions as well as to the proton-to-electron mass ratio. In this connection, the similar Le Roy anomalies (Brown and LeRoy, 1973; Le Roy and Vrscay, 1975) also arising due to the destructive interference in the Lyman and Werner systems are discussed.