| Item type |
デフォルトアイテムタイプ_（フル）(1) |
| 公開日 |
2023-03-18 |
| タイトル |
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タイトル |
The structure of the Calix[4]arene-(H2O) cluster, world’s smallest cup of water |
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言語 |
en |
| 作成者 |
Hontama, Naoya
Inokuchi, Yoshiya
Ebata, Takayuki
Dedonder-Lardeux, Claude
Jouvet, Christophe
Xantheas, Sotiris S.
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| アクセス権 |
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アクセス権 |
open access |
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アクセス権URI |
http://purl.org/coar/access_right/c_abf2 |
| 権利情報 |
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権利情報 |
Copyright (c) 2009 American Chemical Society |
| 主題 |
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主題Scheme |
NDC |
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主題 |
430 |
| 内容記述 |
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内容記述 |
The structure of the calix[4]arene(C4A)-(H2O) cluster formed in a supersonic beam has been investigated by mass-selected resonant two-photon ionization (R2PI) spectroscopy, IR-UV double resonance spectroscopy, IR photodissociation (IRPD) spectroscopy and by high level quantum chemical calculations. The IR-UV double resonance spectrum of C4A-(H2O) exhibits a broad and strong hydrogen-bonded OH stretching band at 3160 cm-1 and a weak asymmetric OH stretching band at 3700 cm-1. The IRPD measurement of the cluster produced a value of 3140 cm-1 for the C4A-(H2O) → C4A + H2O dissociation energy. High level electronic structure calculations at the MP2 level of theory with basis sets up to quadruple zeta quality suggest that the endo-isomer (water inside the C4A cavity) is ~1100 cm-1 more stable than the exo-isomer (water hydrogen bonded to the rim of C4A). The endo-isomer has a best-computed (at the MP2/aug-cc-pVQZ level) value of 3127 cm-1 for the binding energy, just ~15 cm-1 shy of the experimentally determined threshold and an IR spectrum in excellent agreement with the experimentally observed one. In contrast, the B3LYP density functional fails to even predict a stable structure for the endo-isomer demonstrating the inability of that level of theory to describe the delicate balance between structures exhibiting cumulative OH-π H-bonding and dipole-dipole interactions (endo-isomer) when compared to the ones emanating from maximizing the cooperative effects associated with the formation of hydrogen bonded homodromic networks (exo-isomer). The comparison of the experimental results with the ones from high level electronic structure calculations therefore unambiguously assign the endo-isomer as the global minimum of the C4A-(H2O) cluster, world’s smallest cup of water. |
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言語 |
en |
| 内容記述 |
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内容記述タイプ |
Other |
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内容記述 |
This is a preprint of an article published by American Chemical Society in Journal of Physical Chemistry A, 2010, available online: http://pubs.acs.org/doi/abs/10.1021/jp902967q |
| 出版者 |
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出版者 |
American Chemical Society |
| 言語 |
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言語 |
eng |
| 資源タイプ |
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資源タイプ識別子 |
http://purl.org/coar/resource_type/c_6501 |
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資源タイプ |
journal article |
| 出版タイプ |
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出版タイプ |
AO |
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出版タイプResource |
http://purl.org/coar/version/c_b1a7d7d4d402bcce |
| 関連情報 |
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識別子タイプ |
DOI |
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関連識別子 |
10.1021/jp902967q |
| 関連情報 |
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関連タイプ |
isVersionOf |
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識別子タイプ |
DOI |
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関連識別子 |
http://dx.doi.org/10.1021/jp902967q |
| 収録物識別子 |
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収録物識別子タイプ |
ISSN |
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収録物識別子 |
1089-5639 |
| 開始ページ |
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開始ページ |
2967 |
| 書誌情報 |
Journal of Physical Chemistry A
Journal of Physical Chemistry A
巻 114,
号 9,
p. 2967-2972,
発行日 2010-03-11
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| 旧ID |
38061 |
JPhysChemA_2010_114_2967.pdf (6.5 MB)
