Origin of enhanced dihydrogen-metal interaction in carboxylate bridged Cu2-paddle-wheel frameworks

Yong Hyun Kim; Joongoo Kang; Su Huai Wei

doi:10.1103/PhysRevLett.105.236105

Origin of enhanced dihydrogen-metal interaction in carboxylate bridged Cu₂-paddle-wheel frameworks

Yong Hyun Kim, Joongoo Kang, Su Huai Wei

Department of Physics and Chemistry

Research output: Contribution to journal › Article › peer-review

16 Scopus citations

Abstract

The experimentally observed enhancement of hydrogen adsorption in Cu ₂-tetracarboxylate paddle-wheel frameworks is investigated by ab initio density-functional theory calculations. We reveal that the puzzling enhancement is due to the effective orbital coupling between the occupied H ₂ σ and the unoccupied Cu 4s-derived states. The nontrivial dihydrogen-metal σ-s interaction is enabled by a strong localization of the Cu 4s orbital after hybridizing with the neighboring oxygen 2p orbitals. Based on this understanding, we predict that the dihydrogen-metal interaction can be further increased by alloying Cu with s-orbital element Zn or Mg.

Original language	English
Article number	236105
Journal	Physical Review Letters
Volume	105
Issue number	23
DOIs	https://doi.org/10.1103/PhysRevLett.105.236105
State	Published - 3 Dec 2010

Access to Document

10.1103/PhysRevLett.105.236105

Cite this

@article{922db9000ca64301860a1ce638c06c26,

title = "Origin of enhanced dihydrogen-metal interaction in carboxylate bridged Cu2-paddle-wheel frameworks",

abstract = "The experimentally observed enhancement of hydrogen adsorption in Cu 2-tetracarboxylate paddle-wheel frameworks is investigated by ab initio density-functional theory calculations. We reveal that the puzzling enhancement is due to the effective orbital coupling between the occupied H 2 σ and the unoccupied Cu 4s-derived states. The nontrivial dihydrogen-metal σ-s interaction is enabled by a strong localization of the Cu 4s orbital after hybridizing with the neighboring oxygen 2p orbitals. Based on this understanding, we predict that the dihydrogen-metal interaction can be further increased by alloying Cu with s-orbital element Zn or Mg.",

author = "Kim, {Yong Hyun} and Joongoo Kang and Wei, {Su Huai}",

year = "2010",

month = dec,

day = "3",

doi = "10.1103/PhysRevLett.105.236105",

language = "English",

volume = "105",

journal = "Physical Review Letters",

issn = "0031-9007",

publisher = "American Physical Society",

number = "23",

}

TY - JOUR

T1 - Origin of enhanced dihydrogen-metal interaction in carboxylate bridged Cu2-paddle-wheel frameworks

AU - Kim, Yong Hyun

AU - Kang, Joongoo

AU - Wei, Su Huai

PY - 2010/12/3

Y1 - 2010/12/3

N2 - The experimentally observed enhancement of hydrogen adsorption in Cu 2-tetracarboxylate paddle-wheel frameworks is investigated by ab initio density-functional theory calculations. We reveal that the puzzling enhancement is due to the effective orbital coupling between the occupied H 2 σ and the unoccupied Cu 4s-derived states. The nontrivial dihydrogen-metal σ-s interaction is enabled by a strong localization of the Cu 4s orbital after hybridizing with the neighboring oxygen 2p orbitals. Based on this understanding, we predict that the dihydrogen-metal interaction can be further increased by alloying Cu with s-orbital element Zn or Mg.

AB - The experimentally observed enhancement of hydrogen adsorption in Cu 2-tetracarboxylate paddle-wheel frameworks is investigated by ab initio density-functional theory calculations. We reveal that the puzzling enhancement is due to the effective orbital coupling between the occupied H 2 σ and the unoccupied Cu 4s-derived states. The nontrivial dihydrogen-metal σ-s interaction is enabled by a strong localization of the Cu 4s orbital after hybridizing with the neighboring oxygen 2p orbitals. Based on this understanding, we predict that the dihydrogen-metal interaction can be further increased by alloying Cu with s-orbital element Zn or Mg.

UR - http://www.scopus.com/inward/record.url?scp=78649858182&partnerID=8YFLogxK

U2 - 10.1103/PhysRevLett.105.236105

DO - 10.1103/PhysRevLett.105.236105

M3 - Article

AN - SCOPUS:78649858182

SN - 0031-9007

VL - 105

JO - Physical Review Letters

JF - Physical Review Letters

IS - 23

M1 - 236105

ER -

Origin of enhanced dihydrogen-metal interaction in carboxylate bridged Cu₂-paddle-wheel frameworks

Abstract

Access to Document

Other files and links

Fingerprint

Cite this