Fluctuations in intramolecular line shapes—random matrix theory

✍ Scribed by Shaul Mukamel; James Sue; Akhilesh Pandey

• Publisher: Elsevier Science
• Year: 1984
• Tongue: English
• Weight: 480 KB
• Volume: 105
• Category: Article
• ISSN: 0009-2614
• DOI: 10.1016/0009-2614(84)85636-5

✦ Synopsis

Random matrix theory is used to develop a model for the distribution of energy levels and mtensities in intramolecular line shapes. The effects of mikng lines, either due to their weak intensity, or due to the kite spectral resolution, are quantitatively incorporated. It is shown how the information regarding spectral fluctuations in intermediate size molecules is eroded in the large molecule statistical limit. Our predIctions are compared with recent experimental data on highly v~bratlonally excited acetylene, and the relevant skk.~tical measnres are calculated Recent experimental studies of molecular line tiLapes in isolated polyatomlc molecules have generated a vast interest in the statLstical analysis of these spectra [l-5] The purpose of such is to indentify some universal features which will be of interest to a wide class of systems This is in contrast to the traditional analySs which focuses on specific information on a particular molecule (i.e. level positions and dipole