Intermolecular Charge Transfer and Hydrogen Bonding in Solid Furan
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- 作者：Manuel Montejo ; Amparo Navarro ; Gordon J. Kearley ; Juana Vá ; zquez ; and Juan Jesú ; s Ló ; pez-Gonzá ; lez
- 刊名：Journal of the American Chemical Society
- 出版年：2004
- 出版时间：November 24, 2004
- 年：2004
- 卷：126
- 期：46
- 页码：15087 - 15095
- 全文大小：155K
- 年卷期：v.126,no.46(November 24, 2004)
- ISSN：1520-5126
文摘
The calculated structures of furan as a monomer, a dimer that was isolated from the crystalstructure, and the full crystal structure have been thoroughly investigated by a combination of densityfunctional theory (DFT) calculations and inelastic neutron scattering (INS) measurements. To improve ourunderstanding of the nature and magnitude of the intermolecular interactions in the solid, the atoms inmolecules (AIM) theory has been applied to the dimer and a cluster of eight monomers. After a carefultopological study of the theoretical charge density and of its Laplacian, we have established the existenceof C-H···
, C-H···O, and H···H interactions between adjacent molecules in solid furan. The electrondistribution has also been analyzed by performing natural bond orbital (NBO) calculations for the monomerand a H-bonded dimer. When the hydrogen bond is established between two adjacent furan rings, someelectron charge is transferred from the electronic system of one furan ring to the other molecule in thedimer. This result provides a model of the interaction between end groups of neighboring chains of polyfuranand could be applicable to other conjugated polymers where the system is responsible for their conductingproperties. To determine how the intermolecular bonds in the solid affect the vibrational dynamics in theperiodic system, INS data were analyzed by performing molecular and periodic density functionalcalculations. Reasonable agreement is achieved, although we note that the poorest agreement is for modesinvolving hydrogen atoms.
, C-H···O, and H···H interactions between adjacent molecules in solid furan. The electrondistribution has also been analyzed by performing natural bond orbital (NBO) calculations for the monomerand a H-bonded dimer. When the hydrogen bond is established between two adjacent furan rings, someelectron charge is transferred from the electronic system of one furan ring to the other molecule in thedimer. This result provides a model of the interaction between end groups of neighboring chains of polyfuranand could be applicable to other conjugated polymers where the system is responsible for their conductingproperties. To determine how the intermolecular bonds in the solid affect the vibrational dynamics in theperiodic system, INS data were analyzed by performing molecular and periodic density functionalcalculations. Reasonable agreement is achieved, although we note that the poorest agreement is for modesinvolving hydrogen atoms.