Non-adiabatic effects on resonance-enhanced Raman scattering in H2

✍ Scribed by Sima Banerjee; S. S. Bhattacharyya; Samir Saha

• Publisher: John Wiley and Sons
• Year: 1993
• Tongue: English
• Weight: 948 KB
• Volume: 24
• Category: Article
• ISSN: 0377-0486
• DOI: 10.1002/jrs.1250240508

✦ Synopsis

Abstract

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.