Journal of Physical Chemistry, Vol.100, No.45, 17756-17761, 1996
Implications Concerning the Electronic States of Ethylene and Other Olefins from Magnetic Circular-Dichroism Measurements of Tetramethylethylene
An investigation of the electronic excited states of tetramethylethylene in the 240-160 nm region has been carried out using synchrotron radiation for magnetic circular dichroism and absorption spectroscopy. These studies show that there are at least six and probably nine electronic transitions in the region once considered to be the sole domain of the pi --> pi*(B-1(1u)) and pi - 3s(B-1(3u)) transitions. The most likely assignments for the additional four transitions are pi --> 3p(sigma)(B-1(2g)), pi --> 3p(gamma)(B-1(1g)), pi --> 3d(delta)(B-1(2u)), pi --> 3d(delta)(B-1(3u)), or sigma - sigma*. The other three possible electronic transitions are discussed in the paper. These studies also indicate that the positive magnetic circular dichroism bands observed in ethylene are due to an additional electronic transition in the pi --> pi* and pi --> 3s region and not a vibronically induced part of the pi --> 3s transition.
Keywords:CONFIGURATION-INTERACTION CALCULATIONS;SYNCHROTRON RADIATION;EXCITED-STATES;VIBRATIONAL STRUCTURE;IMPACT SPECTROSCOPY;RYDBERG TRANSITIONS;RPA CALCULATIONS;CATIONIC STATES;VUV ABSORPTION;SPECTRA