Structural Evolution of the [(CO2)n(H2O)]- Cluster Anions : Quantifying the Effect of Hydration on the Excess Charge Accommodation Motif
Use this link to cite this item : https://ir.lib.hiroshima-u.ac.jp/00037972
ID | 37972 |
file | |
creator |
Muraoka, Azusa
Hammer, Nathan I.
Shin, Joong-Won
Johnson, Mark A.
Nagata, Takashi
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subject | Infrared photodissociation spectroscopy
cluster anions
structural evolution
hydration
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NDC |
Chemistry
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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., 122, 094303 (2005)]. In the n ≥ 4 spectrum, a pair of intense bands additionally appears at ≈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 ≥ 4.
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description | This is a preprint of an article published by American Chemical Society in Journal of Physical Chemistry A, 2009, available online: http://pubs.acs.org/doi/abs/10.1021/jp903578e.
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journal title |
Journal of Physical Chemistry A
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volume | Volume 113
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issue | Issue 31
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start page | 8942
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end page | 8948
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date of issued | 2009-08-06
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publisher | American Chemical Society
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issn | 1089-5639
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publisher doi | |
pubmed id | |
language |
eng
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nii type |
Journal Article
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HU type |
Journal Articles
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DCMI type | text
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format | application/pdf
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text version | author
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rights | Copyright (c) 2009 American Chemical Society
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relation is version of URL | http://dx.doi.org/10.1021/jp903578e
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department |
Graduate School of Science
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