The structure of the CO2-CO2-H2O van der Waals complex determined by microwave spectroscopy

Rotational spectra of CO2 –CO2 –H2 O, CO2 –CO2 –D2 O, 13 CO2 –13 CO2 –H2 O and CO2 –CO2 –H2 18 O have been measured using a pulsed‐molecular‐beam Fabry–Perot Fourier‐transform microwave spectrometer. An asymmetric top spectrum is observed with rotational constants, A=3313.411(5) MHz, B=1470.548(3) MHz, and C=1308.850(3) MHz for the normal species. The dipole moment obtained is μT =μb =1.989(2) D. Only b‐type transitions are observed with the transitions showing a 3 to 1 intensity alternation depending on whether Ka +Kc is odd or even, respectively. This indicates a structure with twofold symmetry with the C2v axis of the water subunit aligned with the C2 axis of the complex. The CO2 subunits lie in a plane which is perpendicular to the C2 axis and located 2.47 A below the oxygen atom of the water subunit; the C–C bond length is 3.413(2) A. The orientation of the CO2 subunits in CO2 –CO2 –H2 O is very similar to that observed in CO2 –CO2 although the C–C bond length is 0.19 A shorter in the trimer. The C–O...

[1]  R. O. Watts,et al.  High resolution infrared spectrum of acetylene tetramer , 1988 .

[2]  H. S. Gutowsky,et al.  Rotational spectrum and structure of the linear HCN trimer , 1988 .

[3]  C. E. Dykstra,et al.  Torsional vibrational modes of (HF)3: IR–IR double resonance spectroscopy and electrical interaction theory , 1988 .

[4]  K. Jucks,et al.  Near infrared spectroscopic observation of the linear and cyclic isomers of the hydrogen cyanide trimer , 1988 .

[5]  G. T. Fraser,et al.  Structure and vibrational dynamics of the CO2 dimer from the sub‐Doppler infrared spectrum of the 2.7 μm Fermi diad , 1988 .

[6]  H. S. Gutowsky,et al.  Rotational spectra and structures of small clusters containing the HCN dimer: (HCN)2–Ar, a T‐shaped trimer , 1988 .

[7]  J. T. Hougen,et al.  New measurements of microwave transitions in the water dimer , 1987 .

[8]  R. Suenram,et al.  Pulsed beam Fourier transform microwave measurements on OCS and rare gas complexes of OCS with Ne, Ar, and Kr , 1987 .

[9]  G. T. Fraser,et al.  Sub‐Doppler infrared spectrum of the carbon dioxide trimer , 1987 .

[10]  H. S. Gutowsky,et al.  Rotational spectra and structures of the Ar2–H35Cl/37Cl trimers , 1987 .

[11]  William A. Wakeham,et al.  The Forces Between Molecules , 1987 .

[12]  H. S. Gutowsky,et al.  Rotational spectra and structures of the Ar2–H/DF trimers , 1987 .

[13]  D. Millen,et al.  The lengthening of the HF bond on formation of heterodimers B • • • HF: determination and dependence on the strength of the hydrogen bond , 1986, Proceedings of the Royal Society of London. A. Mathematical and Physical Sciences.

[14]  K. I. Peterson,et al.  Structure and internal rotation of H2O–CO2, HDO–CO2, and D2O–CO2 van der Waals complexes , 1984 .

[15]  R. Lord.  Vibrational spectra and structure : Volume 7, J.R. Durig, ed., Elsevier Scientific Publishing Co., Amsterdam, 1978, xv + 388 pages. Dfl. 146,00, $63.50. , 1976 .

[16]  A. Dymanus,et al.  Molecular constants of OCS isotopes in the (0110) vibrational state measured by molecular-beam electric-resonance spectroscopy , 1974 .

[17]  J. Watson.  Determination of Centrifugal Distortion Coefficients of Asymmetric‐Top Molecules , 1967 .

[18]  Edward Teller,et al.  Interaction of the van der Waals Type Between Three Atoms , 1943 .