Mikrowellenspektrum, Struktur und l-Typ-Dublett-Aufspaltung der HCNO (Knallsäure)

Abstract

The microwave spectra of unstable, gaseous fulminic acid H12C14N16O and five of its isotopically substituted species have been studied in the frequency range from 10 to 46 GHz. The spectrum of molecules in the ground vibrational state established the linearity of the chain HCNO. The following rotational constants B0 for the ground state were obtained: B0 (H12C14N16O) = 11 469.04 MHz, B0 (H12C14N17O) = 11 151.69 MHz, B0 (D12C14N16O) = 10 292.51 MHz, B0 (H12C14N18O) = 10 865.34 MHz, B0 (H13C14N16O) = 11 091.57 MHz, B0 (D13C14N16O) = 10 011.18 MHz. From these a combined r8- and r0-structure has been evaluated: r(C—H) = (1.027±0.001) A, r(C—N) = (1.161 ± 0.015) A, r(N—O) = (1.207±0.015) A. The rather large uncertainties in the C—N- and N—O-distances are due to the proximity of the N-atom to the center of gravity. It appears to be the first time that, in the same molecule, two different ι-type doublets (Δl=0, AJ= + 1) and their corresponding series of /-type doubling transitions (Al =2, ΔJ = 0), arising from the two degenerate bending modes (υ4=1 and v5=1), have been observed. The analysis of the two ι-type doubling series revealed a marked dependence of the /-type doubling constants q4 and q5 on higher powers of the angular momentum J. This J-dependence was found to be substantially different for the two vibrational modes. The doubling constants given in MHz are q4=23.6722 - (0.6139·10-3) J(J+1) + (0.1417·10-6) [J(J+1)]2-(0199·10-10) [J(J+1)]3, q5=34.6391 - (0.1623·10-3) J(J+1) + (1.00·10-9) [J(J+1)]2. The molecular dipole moment was determined from Stark-effect measurements on the J=0 → 1 transition in the ground state and found to be (3.06 ± 0.15) Debye. The nuclear quadrupole coupling constants for the 14N- and 170-nuclei can be given as e q Q (17O) = — (12.31 ± 0.12) MHz and | e q Q (14N) | ≦ 0.3 MHz.