화학공학소재연구정보센터
Journal of Chemical Physics, Vol.121, No.1, 237-247, 2004
Nuclear quadrupole hyperfine structure in the microwave spectrum of HCl-N2O: Electric field gradient perturbation of N2O by HCl
The microwave spectra of six isotopomers of HCl-N2O have been obtained in the 7-19 GHz region with a pulsed molecular beam, Fourier transform microwave spectrometer. The nuclear quadrupole hyperfine structure due to all quadrupolar nuclei is resolved and the spectra are analyzed using the Watson S-reduced Hamiltonian with the inclusion of nuclear quadrupole coupling interactions. The spectroscopic constants determined include rotational constants, quartic and sextic centrifugal distortion constants, and nuclear quadrupole coupling constants for each quadrupolar nucleus. Due to correlations of the structural parameters, the effective structure of the complex cannot be obtained by fitting to the spectroscopic constants of the six isotopomers. Instead, the parameters for each isotopomer are calculated from the A and C rotational constants and the chlorine nuclear quadrupole coupling constant along the a-axis, chi(aa). There are two possible structures; the one in which hydrogen of HCl interacts with the more electronegative oxygen of N2O is taken to represent the complex. The two subunits are approximately slipped parallel. For H Cl-35-(N2O)-N-14, the distance between the central nitrogen and chlorine is 3.5153 Angstrom and the N2O and HCl subunits form angles of 72.30degrees and 119.44degrees with this N-Cl axis, respectively. The chlorine and oxygen atoms occupy the opposite, obtuse vertices of the quadrilateral formed by O, central N, Cl, and H. Nuclear quadrupole coupling constants show that while the electric field gradient of the HCl subunit remains essentially unchanged upon complexation, there is electronic rearrangement about the two nitrogen nuclei in N2O. (C) 2004 American Institute of Physics.