HIGH-RESOLUTION INFRARED SPECTRA OF BICYCLO[1.1.1]PENTANE: ANALYSES OF THE \nub{14}(e') AND \nub{18}($a_2$") BANDS
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Date
2010
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Publisher
Ohio State University
Abstract
Infrared spectra of the \nub{14}(e') 540 \wn ~and \nub{18}($a_2$") 835 \wn ~bands of bicyclo[1.1.1]pentane have been recorded at a resolution sufficient (0.0015 \wn) to resolve for the first time individual rovibrational lines. This report presents the ground state constants for this molecule determined from two of the ten infrared-active fundamental bands. The fitted transitions were judged to be free of perturbations of their upper state levels. A combined total of more than 6000 lines with $J$ and $K$ quantum numbers of the two bands ranging up to about 60 were fit with an obs-calc RMS deviation of 0.00021 \wn. ~The following principal constants (in units of \wn) of the rovibrational ground state were obtained: $B_0$ = 0.23994136(30), $D_J$ = 5.9959(96)x$10^{-8}$, ~and $D_{JK}$ = -1.5052(98)x$10^{-8}$. The band centers were found to be \nub{14} = 540.326397(19) \wn ~and \nub{18} = 832.92902(3) \wn. The values in parentheses represent the uncertainties (2 standard deviations) in the last digits of the value of the constants. The results are compared with those obtained for [1.1.1]propellane and with those computed at the ab initio anharmonic level using the B3LYP density functional method with a cc-pVTZ basis set.
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Author Institution: Department of Chemistry, Oregon State University, Corvallis, OR, 97332-4003, USA; Department of Chemistry and Biochemstry, California State University; East Bay, Hayward, CA, 94542, USA; Department of Chemistry, Oregon State University, Corvallis, OR, 97332-4003, USA; Department of Chemistry, Oregon State University, Corvallis, OR, 97332-4003, USA; Optical Technology Division, National Institute of Standards and; Technology,Gaithersburg, MD, 20899-8441, USA; 15012 24th Ave., S.E., Mill Creek, WA, 98012, USA; Pacific Northwest National Laboratory, P.O. BOX 999, Mail Stop K8-88; Richland, WA,USA