Spectroscopic identification of carbon dioxide clusters: (CO2)6 to (CO2)13.

In spite of wide interest in CO(2) clusters, only dimers and trimers have previously been assigned to specific infrared bands. Here, transitions for clusters with 6-13 molecules are identified in the ν(3) region (∼2350 cm(-1)). Spectra are observed in a supersonic jet (T ∼ 2.5 K) using a tunable laser probe, and analyzed with the aid of cluster calculations based on a widely-used model potential. Vibrational origins show blue-shifts significantly larger than predicted by resonant dipole interactions.

[1]  M. Klein,et al.  Ab initio molecular dynamics study of supercritical carbon dioxide including dispersion corrections. , 2009, The Journal of chemical physics.

[2]  R. Signorell,et al.  Infrared spectra of C2H6, C2H4, C2H2, and CO2 aerosols potentially formed in Titan's atmosphere. , 2009, The journal of physical chemistry. A.

[3]  Hiroshi Takeuchi,et al.  Geometry optimization of carbon dioxide clusters (CO2)n for 4 < or = n < or = 40. , 2008, The journal of physical chemistry. A.

[4]  K. Jose,et al.  An ab initio investigation on (CO2)n and CO2(Ar)m clusters: geometries and IR spectra. , 2008, The Journal of chemical physics.

[5]  N. Moazzen-Ahmadi,et al.  The cyclic CO2 trimer: observation of a parallel band and determination of an intermolecular out-of-plane torsional frequency. , 2008, The Journal of chemical physics.

[6]  Z. Abusara,et al.  Isotope effects in the infrared spectra of the polar and nonpolar isomers of N2O dimer , 2008 .

[7]  H. Huber,et al.  Beyond the resonant dipole interaction model: resolution of a discrepancy between experimental and calculated structures of the carbon dioxide cyclic planar trimer. , 2006, The Journal of chemical physics.

[8]  R. Georges,et al.  IR signature of (CO2)N clusters: size, shape and structural effects. , 2005, Physical chemistry chemical physics : PCCP.

[9]  H. Liu,et al.  Finite temperature properties of (CO 2 ) n clusters , 2003 .

[10]  R. Georges,et al.  Infrared spectroscopy of (CO2)N nanoparticles (30 , 2003 .

[11]  R. Signorell.  Verification of the vibrational exciton approach for CO2 and N2O nanoparticles , 2003 .

[12]  Joseph M. DeSimone,et al.  Practical Approaches to Green Solvents , 2002, Science.

[13]  C. Weitkamp,et al.  Liquid-helium temperature long-path infrared spectroscopy of molecular clusters and supercooled molecules , 2001 .

[14]  E. Vogel,et al.  A new intermolecular potential energy surface for carbon dioxide from ab initio calculations , 2000 .

[15]  H. Lüthi,et al.  HIGH-LEVEL AB INITIO COMPUTATIONS OF STRUCTURES AND RELATIVE ENERGIES OF TWO ISOMERS OF THE CO2 TRIMER , 1999 .

[16]  Jean-Bernard Maillet,et al.  FROM MOLECULAR CLUSTERS TO BULK MATTER. II. CROSSOVER FROM ICOSAHEDRAL TO CRYSTALLINE STRUCTURES IN CO2 CLUSTERS , 1999 .

[17]  Betsy M. Rice,et al.  Intermolecular potential of carbon dioxide dimer from symmetry-adapted perturbation theory , 1999 .

[18]  B. Kirchner,et al.  Structural and thermodynamic properties of fluid carbon dioxide from a new ab initio potential energy surface , 1998 .

[19]  D. Nesbitt,et al.  Geometric isomerism in clusters: High resolution infrared spectroscopy of a noncyclic CO2 trimer , 1996 .

[20]  M. F. Feraudy,et al.  Structural transformation in (CO2)N clusters, N<100 , 1996 .

[21]  R. Saykally,et al.  Water Clusters , 1996, Science.

[22]  Jeanette M. Sperhac,et al.  High‐resolution infrared diode laser spectroscopy of (CO2)3: Vibrationally averaged structures, resonant dipole vibrational shifts, and tests of CO2–CO2 pair potentials , 1995 .

[23]  G. Ewing,et al.  Large CO2 clusters studied by infrared spectroscopy and light scattering , 1993 .

[24]  T. E. Gough,et al.  The infrared spectrum of clustered carbon dioxide: An interpretation via bulk optical constants , 1991 .

[25]  John S. Muenter,et al.  An intermolecular potential function model applied to acetylene dimer, carbon dioxide dimer, and carbon dioxide acetylene , 1991 .

[26]  M. Klein,et al.  Structure and dynamics of carbon dioxide clusters: a molecular dynamics study , 1989 .

[27]  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 .

[28]  B. Howard,et al.  Pulsed molecular beam infrared absorption spectroscopy of CO2 dimer , 1987 .

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

[30]  T. E. Gough,et al.  Fourier transform infrared spectroscopy of molecular clusters: The structure and internal mobility of clustered carbon dioxide , 1987 .

[31]  I. R. Mcdonald,et al.  Electrostatic interactions in molecular crystals , 1983 .

[32]  B. W. V. D. Waal.  Calculated ground‐state structures of 13‐molecule clusters of carbon dioxide, methane, benzene, cyclohexane, and naphthalene , 1983 .

[33]  R. Pan,et al.  Thermodynamic properties and phase transitions in CO2 molecular clusters , 1981 .