ISSN:
1089-7690
Source:
AIP Digital Archive
Topics:
Physics
,
Chemistry and Pharmacology
Notes:
Propargylene was identified in a matrix as a product of photolysis of cyclopropenylidene and diazopropyne. The molecule is a triplet. The optimum geometry predicted by ab initio calculations corresponds to a structure HC≡C–C¨H. The transition structure in the interconversion HC≡C–C¨H(arrow-right-and-left)HC(overdot)=C=C(overdot)H(arrow-right-and-left)HC¨–C≡CH is very low in energy and close to the energy of the vibrational ground state. Owing to this nonrigidity, computed infrared (IR) frequencies based on a harmonic treatment do not match the experimental spectrum. When this nonrigidity is taken into account by using a nonharmonic approximation calculated UMP2/6-31G** IR spectra are in good agreement with the observed spectra of HCCCH and DCCCD.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1063/1.456765
