Microwave Fourier transform spectrum of the water-carbonyl sulfide complex.
The microwave spectrum of the water-carbonyl sulfide complex H(2)O-OCS was observed with a pulsed-beam, Fabry-Perot cavity Fourier-transform microwave spectrometer. In addition to the normal isotopic form, we also measured the spectra of H(2)O-S(13)CO, H(2)O-(34)SCO, H(2) (18)O-SCO, D(2)O-SCO, D(2)O-S(13)CO, D(2)O-(34)SCO, HDO-SCO, HDO-S(13)CO, and HDO-(34)SCO. The rotational constants are B = 1522.0115(2) MHz and C = 1514.3302(2) MHz for H(2)O-SCO; B = 1511.9153(5) MHz and C = 1504.3346(5) MHz for H(2)O-S(13)CO; B = 1522.0215(3) MHz and C = 1514.3409(3) MHz for H(2)O-(34)SCO; B = 1435.9571(3) MHz and C = 1429.1296(4) MHz for H(2) (18)O-SCO, B = 1409.6575(5) MHz and C = 1397.9555(5) MHz for D(2)O-SCO; B = 1399.8956(3) MHz and C = 1388.3543(3) MHz for D(2)O-S(13)CO; B = 1409.6741(24) MHz and C = 1397.9775(24) MHz for D(2)O-(34)SCO; (B+C)/2 = 1457.9101(2) MHz for HDO-SCO; (B + C)/2 = 1448.0564(4) MHz for HDO-S(13)CO; and (B+C)/2 = 1457.9418(15) MHz for HDO-(34)SCO, with uncertainties corresponding to one standard deviation. The observed rotational constants for the sulfur-34 complexes are generally higher than those for the corresponding sulfur-32 isotopomers. The heavier isotopomers have smaller effective moments of inertia due to the smaller vibrational amplitude of the (34)S-C vibration (zero point) as compared to the (32)S-C, making the effective O-(34)S bond slightly shorter. Stark effect measurements for H(2)O-SCO give a dipole moment of 8.875(9)x10(-30) C m [2.6679(28) D]. The most probable structure of H(2)O-SCO is near C(2v) planar with the oxygen of water bonded to the sulfur of carbonyl sulfide. The oxygen-sulfur van der Waals bond length is determined to be 3.138(17) A, which is very close to the ab initio value of 3.144 A. The structures of the isoelectronic complexes H(2)O-SCO, H(2)O-CS(2), H(2)O-CO(2), and H(2)O-N(2)O are compared. The first two are linear and the others are T shaped with an O-C/O-N van der Waals bond, i.e., the oxygen of water bonds to the carbon and nitrogen of CO(2) and N(2)O, respectively.
Tatamitani
Yoshio
Y
Department of Chemistry, Faculty of Science, Shizuoka University, Ohya, Shizuoka 422-5829, Japan.
Ogata
Teruhiko
T