Electronic structure and molecular properties of the mixed rhenium-molybdenum [Re6-x Mo x S8(CN) 6]q-, (x = 0 to 6) Clusters

R. Ramírez-Tagle; R. Arratia-Pérez

doi:10.1007/s10876-008-0213-6

Electronic structure and molecular properties of the mixed rhenium-molybdenum [Re_6-x Mo _x S₈(CN) ₆]^q-, (x = 0 to 6) Clusters

R. Ramírez-Tagle
, R. Arratia-Pérez

Universidad Andres Bello

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

7 Scopus citations

Abstract

Relativistic density functional calculations including scalar and spin-orbit effects via the ZORA approximation and including solvent effects were carried out on the [Re₆S₈(CN)₆]^4-, [Re₅MoS₈(CN)₆]^5-, [Re ₄Mo₂S₈(CN)₆]^5-, [Re ₃Mo₃S₈(CN)₆]^5-, [Re ₂Mo₄S₈(CN)₆]^5-, [ReMo₅S₈(CN)₆]^5- and [Mo ₆S₈(CN)₆]^6- clusters. By increasing the replacement of each Re atom with Mo atoms we find that for x > 2 the HOMO-LUMO gap decreases significantly. The calculated gap of the [Re ₃Mo₃S₈(CN)₆]^5-, [Re ₂Mo₄S₈(CN)₆]^5- and [ReMo₅S₈(CN)₆]^5- clusters is similar to the calculated and observed gap of the superconducting PbMo ₆S₈ Chevrel phases. The current calculations also indicates that the electronic similarities of the lowest excited states of the semiconducting 24e [Re₅MoS₈(CN)₆]^5- and 23e [Re₄Mo₂S₈(CN)₆]^5- clusters with the strongly luminescent 24e [Re₆S₈(CN) ₆]^4- cluster, suggest that these mixed metal clusters might be luminescent.

Original language	English
Pages (from-to)	159-164
Number of pages	6
Journal	Journal of Cluster Science
Volume	20
Issue number	1
DOIs	https://doi.org/10.1007/s10876-008-0213-6
State	Published - Mar 2009
Externally published	Yes

Keywords

Mixed Re-Mo clusters
Relativistic Effects

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title = "Electronic structure and molecular properties of the mixed rhenium-molybdenum [Re6-x Mo x S8(CN) 6]q-, (x = 0 to 6) Clusters",

abstract = "Relativistic density functional calculations including scalar and spin-orbit effects via the ZORA approximation and including solvent effects were carried out on the [Re6S8(CN)6]4-, [Re5MoS8(CN)6]5-, [Re 4Mo2S8(CN)6]5-, [Re 3Mo3S8(CN)6]5-, [Re 2Mo4S8(CN)6]5-, [ReMo5S8(CN)6]5- and [Mo 6S8(CN)6]6- clusters. By increasing the replacement of each Re atom with Mo atoms we find that for x > 2 the HOMO-LUMO gap decreases significantly. The calculated gap of the [Re 3Mo3S8(CN)6]5-, [Re 2Mo4S8(CN)6]5- and [ReMo5S8(CN)6]5- clusters is similar to the calculated and observed gap of the superconducting PbMo 6S8 Chevrel phases. The current calculations also indicates that the electronic similarities of the lowest excited states of the semiconducting 24e [Re5MoS8(CN)6]5- and 23e [Re4Mo2S8(CN)6]5- clusters with the strongly luminescent 24e [Re6S8(CN) 6]4- cluster, suggest that these mixed metal clusters might be luminescent.",

keywords = "Mixed Re-Mo clusters, Relativistic Effects",

author = "R. Ram{\'i}rez-Tagle and R. Arratia-P{\'e}rez",

year = "2009",

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doi = "10.1007/s10876-008-0213-6",

language = "English",

volume = "20",

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journal = "Journal of Cluster Science",

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AU - Ramírez-Tagle, R.

AU - Arratia-Pérez, R.

PY - 2009/3

Y1 - 2009/3

N2 - Relativistic density functional calculations including scalar and spin-orbit effects via the ZORA approximation and including solvent effects were carried out on the [Re6S8(CN)6]4-, [Re5MoS8(CN)6]5-, [Re 4Mo2S8(CN)6]5-, [Re 3Mo3S8(CN)6]5-, [Re 2Mo4S8(CN)6]5-, [ReMo5S8(CN)6]5- and [Mo 6S8(CN)6]6- clusters. By increasing the replacement of each Re atom with Mo atoms we find that for x > 2 the HOMO-LUMO gap decreases significantly. The calculated gap of the [Re 3Mo3S8(CN)6]5-, [Re 2Mo4S8(CN)6]5- and [ReMo5S8(CN)6]5- clusters is similar to the calculated and observed gap of the superconducting PbMo 6S8 Chevrel phases. The current calculations also indicates that the electronic similarities of the lowest excited states of the semiconducting 24e [Re5MoS8(CN)6]5- and 23e [Re4Mo2S8(CN)6]5- clusters with the strongly luminescent 24e [Re6S8(CN) 6]4- cluster, suggest that these mixed metal clusters might be luminescent.

AB - Relativistic density functional calculations including scalar and spin-orbit effects via the ZORA approximation and including solvent effects were carried out on the [Re6S8(CN)6]4-, [Re5MoS8(CN)6]5-, [Re 4Mo2S8(CN)6]5-, [Re 3Mo3S8(CN)6]5-, [Re 2Mo4S8(CN)6]5-, [ReMo5S8(CN)6]5- and [Mo 6S8(CN)6]6- clusters. By increasing the replacement of each Re atom with Mo atoms we find that for x > 2 the HOMO-LUMO gap decreases significantly. The calculated gap of the [Re 3Mo3S8(CN)6]5-, [Re 2Mo4S8(CN)6]5- and [ReMo5S8(CN)6]5- clusters is similar to the calculated and observed gap of the superconducting PbMo 6S8 Chevrel phases. The current calculations also indicates that the electronic similarities of the lowest excited states of the semiconducting 24e [Re5MoS8(CN)6]5- and 23e [Re4Mo2S8(CN)6]5- clusters with the strongly luminescent 24e [Re6S8(CN) 6]4- cluster, suggest that these mixed metal clusters might be luminescent.

KW - Mixed Re-Mo clusters

KW - Relativistic Effects

UR - https://www.scopus.com/pages/publications/67349280227

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DO - 10.1007/s10876-008-0213-6

M3 - Article

AN - SCOPUS:67349280227

SN - 1040-7278

VL - 20

SP - 159

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JO - Journal of Cluster Science

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IS - 1

ER -

Electronic structure and molecular properties of the mixed rhenium-molybdenum [Re_6-x Mo _x S₈(CN) ₆]^q-, (x = 0 to 6) Clusters

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Keywords

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