Rotational Spectrum of Vinylarsine.

The rotational spectrum of vinylarsine in the ground state has been studied in the range 7-320 GHz. The spectra of a syn conformer and a gauche conformer have been unambiguously assigned on the basis of the existence of a b-type or a c-type spectrum. Rotational constants, quartic, and some sextic centrifugal distortion constants were derived. For the syn form, measurements of low J aR0,1 transitions in a pulsed-nozzle Fourier transform microwave spectrometer (FTMWS) enabled the determination of the diagonal elements of the quadrupole tensor, as well as two spin-rotation constants. Ab initio calculations performed at the MP2 level using the 6-311++G(3df, 3pd) basis set reproduced experimental rotational constants within 0.2%. Copyright 1998 Academic Press.

Rotational Spectra of the Isotopic Species of Chloroform: Experimental and Ab Initio Structures.

The millimeter-wave spectra of three different samples of chloroform (CHCl3, CDCl3, and 13CHCl3) have been measured between 145 and 470 GHz which corresponds to J values between 22 and 70. We report accurate rotational and centrifugal distortion constants for the ground vibrational states of 11 isotopic species. The experimental ro, rs, rIepsilon, rrhom, and rz structures have been determined using the determined rotational constants. The structure has also been calculated ab initio at the SCF, MP2, RQCISD, and B3LYP levels using triple zeta polarized basis sets. The experimental results are found in excellent agreement with the ab initio predictions. An approximate equilibrium structure has been obtained by combining the experimental results and the ab initio calculations: re(C-H) = 1.080 (2) Å, re(C-Cl) = 1.760 (2) Å, and anglee(HCCl) = 108.23 (2) degrees. Copyright 1998 Academic Press.