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Title: THE 1670 {\AA} TRANSITION OF trans-BUTENE-2
Creators: McDiarmid, R.
Issue Date: 1967
Publisher: Ohio State University
Abstract: The quantum defect calculated when the origin of the sharply structured system of intense absorption bands lying to the blue of the broad $\pi^{\ast} \leftarrow \pi$ transition of trans-butene-2 is fitted to the Rydberg equation with an assumed ionization potential of 9,11 eV is found to be comparable with that obtained for transitions to ns Rydberg states of ethylene: t-butene-1.16; ethylene-1.09. The zero point energy shift between the systems origins in t-butene and perdeutero-t-butene is also comparable with that observed between light and heavy ethylene: $-230 cm^{-1} vs - 180 cm^{-1}$. From these we conclude that the $1670 {\AA}$ transition of t-butene-2 is the transition to the 4s Rydberg state of this molecule. A comparison between the vibrational frequency intervals observed in t-butene-2 and perdeutero-t-butene-2 affords an approximate description of the motions responsible for the stronger vibronic bands. A further comparison between the frequency intervals observed in the 4s Rydberg state and those reported for the ground state of the light compound indicates that the carbon-carbon double bond and the $sp^{2}$ carbon-hydrogen bonds are weaker in the 4s Rydberg state than in the ground state but that the $sp^{2}$ $carbon-sp^{3}$ carbon bonds are stronger in the Rydberg state. The vibrational structure of the $1670 {\AA}$ transition was observed to differ from that observed in the $2000 {\AA}$ transition, suggesting that the latter is not the missing first member of the Rydberg series.
Description: Author Institution: National Institutes of Health
Other Identifiers: 1967-H-10
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