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Non‐adiabatic effects on resonance‐enhanced Raman scattering in H 2
Author(s) -
Banerjee Sima,
Bhattacharyya S. S.,
Saha Samir
Publication year - 1993
Publication title -
journal of raman spectroscopy
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.748
H-Index - 110
eISSN - 1097-4555
pISSN - 0377-0486
DOI - 10.1002/jrs.1250240508
Subject(s) - adiabatic process , excitation , raman spectroscopy , excited state , raman scattering , atomic physics , chemistry , resonance (particle physics) , spectral line , molecular physics , physics , optics , quantum mechanics
Resonance‐enhanced Raman scattering (RERS) from the ground X 1 Σ g + (ν g = 0, J g ) state of H 2 via the excited intermediate C 1 Π u (ν = 0/1/2/3, J i ) state coupled non‐adiabatically with the B 1 Σ u + (ν iB = 8/10/12/14, J i ) state was studied theoretically, applying second‐order perturbation theory. The excitation and Raman spectra for the pure rotational, fundamental and higher overtones are presented. Effects of non‐adiabatic coupling on the excitation profiles, scattered intensities and depolarization ratios were investigated. The intensities of excitation spectra and Raman lines for O ‐, Q ‐ and S ‐branches were calculated using thermal Boltzmann factors for vibrational–rotational distribution at room temperature (300 K). The RERS cross‐sections with adiabatic and non‐adiabatic corrections are reported together with Born–Oppenheimer (BO) results where available, for comparison. The calculated RERS cross‐sections including non‐adiabatic effects were found to vary significantly from adiabatic or BO results.