title: Structural evolution of the [(CO2)n(H2O)]- cluster anions: quantifying the effect of hydration on the excess charge accommodation motif.
abstract: The [(CO2)n(H2O)]- cluster anions are studied using infrared photodissociation (IPD) spectroscopy in the 2800-3800 cm(-1) range. The observed IPD spectra display a drastic change in the vibrational band features at n = 4, indicating a sharp discontinuity in the structural evolution of the monohydrated cluster anions. The n = 2 and 3 spectra are composed of a series of sharp bands around 3600 cm(-1), which are assignable to the stretching vibrations of H2O bound to C2O4- in a double ionic hydrogen-bonding (DIHB) configuration, as was previously discussed (J. Chem. Phys. 2005, 122, 094303). In the n > or = 4 spectrum, a pair of intense bands additionally appears at approximately 3300 cm(-1). With the aid of ab initio calculations at the MP2/6-31+G* level, the 3300 cm(-1) bands are assigned to the bending overtone and the hydrogen-bonded OH vibration of H2O bound to CO2- via a single O-H...O linkage. Thus, the structures of [(CO2)n(H2O)]- evolve with cluster size such that DIHB to C2O4- is favored in the smaller clusters with n = 2 and 3 whereas CO2- is preferentially stabilized via the formation of a single ionic hydrogen-bonding (SIHB) configuration in the larger clusters with n > or = 4.
authors: Department of Basic Science, Graduate School of Arts and Sciences, The University of Tokyo, Komaba, Meguro-ku, Tokyo 153-8902, Japan.
authors: Azusa
authors: A
authors: Muraoka
authors: Yoshiya
authors: Y
authors: Inokuchi
authors: Nathan I
authors: NI
authors: Hammer
authors: Joong-Won
authors: JW
authors: Shin
authors: Mark A
authors: MA
authors: Johnson
authors: Takashi
authors: T
authors: Nagata