Vibration–rotation interactions in H2, HD and D2: centrifugal distortion factors and the derivatives of polarisability invariants

Ankit Raj, Henryk A. Witek*, Hiro o. Hamaguchi

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

1 Scopus citations


We report the correction factors for centrifugal distortion in Raman intensities for pure rotation (O0- and S0-branch) and vibration–rotation (O1- and S1-branch) transitions in the ground electronic state of H2, HD and D2. These factors are presented for 52 selected excitation wavelengths and for the initial rotational states, J = 2 - 21. This data is useful in applications of intensity calibration of spectrometers and the spectroscopy of flames. The classical treatment of centrifugal distortion involved the expansion of polarisability anisotropy (γ) over the internuclear distance, while assuming the diatomic molecule behaves as a harmonic oscillator. Here, this approximation of polarisability invariants as a Taylor series expansion is tested, revealing that truncation up to the second-order derivatives of mean polarisability (α¯) and polarisability anisotropy (γ) gives faithful representations, yielding accurate expectation values with error < 0.2%, for the ground rovibrational state and for the fundamental transition.

Original languageEnglish
Article numbere1632950
JournalMolecular Physics
Issue number5
StatePublished - 2 Jul 2019


  • Polarisability
  • Raman spectroscopy
  • hydrogen molecule
  • polarisability invariants

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