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Identify the precise instrumental broadening contribution in line-width analysis

Ascertain the precise instrumental contribution to Gaussian line-width broadening in the rapid-scan optical parametric oscillator slit-jet spectroscopy of (D2O)2, so that Lorentzian predissociation broadening and any J-dependence can be reliably separated when estimating upper-state lifetimes.

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Background

Line widths were modeled using a Gaussian instrumental profile plus Lorentzian lifetime broadening, but the exact instrumental contribution is not quantified, introducing uncertainty in deduced lifetimes.

Separating instrumental and physical broadening components is essential for accurate determination of predissociation lifetimes and for understanding their dependence on symmetry and rotational quantum numbers.

References

These Lorentzian widths are only approximate (especially in Table II) because we do not know the precise instrumental contribution and because there may also be J-dependence, but they are still meaningful, especially relative to each other.

— Spectra of the D2O dimer in the O-D fundamental stretch region: the acceptor symmetric stretch fundamental and new combination bands (2402.14923 - Barclay et al., 22 Feb 2024) in Section IV.B (Line widths and vibrational shifts)