Structure of Protonated Carbon Dioxide Clusters:  Infrared Photodissociation Spectroscopy and ab Initio Calculations

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 112; no. 5; pp. 950 - 959
• Main Authors: Douberly, G. E, Ricks, A. M, Ticknor, B. W, Duncan, M. A
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 07.02.2008
• Subjects: Carbon Dioxide - chemistry; Computational Biology; Mass Spectrometry; Models, Molecular; Molecular Conformation; Photochemistry; Protons; Spectrophotometry, Infrared; Vibration
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp7098587

The infrared photodissociation spectra (IRPD) in the 700 to 4000 cm-1 region are reported for H+(CO2) n clusters (n = 1−4) and their complexes with argon. Weakly bound Ar atoms are attached to each complex upon cluster formation in a pulsed electric discharge/supersonic expansion cluster source. An expanded IRPD spectrum of the H+(CO2)Ar complex, previously reported in the 2600−3000 cm-1 range [Dopfer, O.; Olkhov, R.V.; Roth, D.; Maier, J.P. Chem. Phys. Lett. 1998, 296, 585−591] reveals new vibrational resonances. For n = 2 to 4, the vibrational resonances involving the motion of the proton are observed in the 750 to 1500 cm-1 region of the spectrum, and by comparison to the predictions of theory, the structure of the small clusters are revealed. The monomer species has a nonlinear structure, with the proton binding to the lone pair of an oxygen. In the dimer, this nonlinear configuration is preserved, with the two CO2 units in a trans configuration about the central proton. Upon formation of the trimer, the core CO2 dimer ion undergoes a rearrangement, producing a structure with near C 2 v symmetry, which is preserved upon successive CO2 solvation. While the higher frequency asymmetric CO2 stretch vibrations are unaffected by the presence of the weakly attached Ar atom, the dynamics of the shared proton motions are substantially altered, largely due to the reduction in symmetry of each complex. For n = 2 to 4, the perturbation due to Ar leads to blue shifts of proton stretching vibrations that involve motion of the proton mostly parallel to the O−H+−O axis of the core ion. Moreover, proton stretching motions perpendicular to this axis exhibit smaller shifts, largely to the red. Ab initio (MP2) calculations of the structures, complexation energies, and harmonic vibrational frequencies are also presented, which support the assignments of the experimental spectra.