标题：Radiationless relaxation in “large” molecules: Experimental evidence for preparation of true molecular eigenstates and Born-Oppenheimer states by a coherent light source
期刊名称：Proceedings of the National Academy of Sciences
印刷版ISSN：0027-8424
电子版ISSN：1091-6490
出版年度：1977
卷号：74
期号：4
页码：1310-1314
DOI：10.1073/pnas.74.4.1310
语种：English
出版社：The National Academy of Sciences of the United States of America
摘要：Photon absorption and emission by molecules that undergo radiationless transitions are examined using the single modes of lasers having well-defined coherence properties. Contrary to the usual beliefs, where it is assumed that the molecule is prepared in a Born-Oppenheimer singlet state and then "crosses-over" to other states (vibrationally "hot" singlets and/or triplets), it is shown experimentally that the true eigenstates of the molecule can be prepared, even in "large" molecules, if the laser correlation time is relatively long and the molecular relaxation is made slow. On the other hand, lasers with short (psec) correlation time have yielded effectively the singlet Born-Oppenheimer state, which has a much shorter lifetime than the true eigenstates. Effects of magnetic fields and temperature are also reported. The former changes the amount of mixing amongst the Born-Oppenheimer states. The latter, on the other hand, swings the molecule from being "small" (i.e., sparse vibronic structure with long lifetimes) to being "large" (i.e., dense statistical distribution of levels) since the relaxation between levels is very effective at high temperatures. Finally, the results of this work show that the words fluorescence and phosphorescence in their strict meaning are misleading if the true eigenstates, which may contain both singlet and triplet character, are prepared.
关键词：radiationless transitions ; optical coherence ; resonance decay of excited states ; laser spectroscopy
