The Vegard-Kaplan band and the phosphorescent decay of N2

✍ Scribed by Jeppe Olsen; Boris Minaev; Olav Vahtras; Hans Ågren; Poul Jørgensen; Hans Jørgen Aa. Jensen; Trygve Helgaker

• Publisher: Elsevier Science
• Year: 1994
• Tongue: English
• Weight: 728 KB
• Volume: 231
• Category: Article
• ISSN: 0009-2614
• DOI: 10.1016/0009-2614(94)01300-4

✦ Synopsis

The phosphorescence transition A 'L5: -tX 'x2 in Nz is studied by quadratic response and multi-configuration self-consistent field theory. Using full valence correlation reference wavefunctions, response theory predicts the total radiative lifetime of the (u' =0) A 'Cc, state (the C= 1 component) to 2.58 s and the corresponding averaged radiative lifetime to 3.87 s, to be compared with the experimental averaged value of 1.9 s. Though there is a systematic overestimation of the lifetime, the theoretical phosphorescence transition moment curve and the relative vibronic intensities are in good agreement with experiment. A novel derivation of the relation between an induced transition moment and a residue of the quadratic response function is presented.