Theoretical study of the pseudo-jahn-teller effect in the edge-sharing bioctahedral complex Mo2(DXyIF)2(O2CCH 3)2(μ2-O)2

Justyna M. Zurek; Martin J. Paterson

doi:10.1021/ic901285f

Theoretical study of the pseudo-jahn-teller effect in the edge-sharing bioctahedral complex Mo₂(DXyIF)₂(O₂CCH ₃)₂(μ₂-O)₂

Justyna M. Zurek, Martin J. Paterson

School of Engineering & Physical Sciences

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

10 Citations (Scopus)

Abstract

A study of the D_2h to C_2h pseudo-Jahn-Teller distortion in the edge-sharing bioctahedral complex Mo₂(DXyIF) ₂(O₂CCH₃)₂(µ₂-O) ₂ is presented. We have performed extensive density functional theory (DFT) and complete active space self-consistent field (CASSCF) calculations. For both the full target complex and a model derived by replacing xylyl and methyl groups with hydrogens we observe that the central Mo₂(µ ₂-O)₂ motif displays C_2h rather than D _2h symmetry. Analytical CASSCF frequency calculations prove that the rhomboidal distortion of the complex from D_2h to C_2h is due to a vibronic mixing of the ground electronic state and a low-lying pd* excited state. © 2009 American Chemical Society.

Original language	English
Pages (from-to)	10652-10657
Number of pages	6
Journal	Inorganic Chemistry
Volume	48
Issue number	22
DOIs	https://doi.org/10.1021/ic901285f
Publication status	Published - 16 Nov 2009

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title = "Theoretical study of the pseudo-jahn-teller effect in the edge-sharing bioctahedral complex Mo2(DXyIF)2(O2CCH 3)2(μ2-O)2",

abstract = "A study of the D2h to C2h pseudo-Jahn-Teller distortion in the edge-sharing bioctahedral complex Mo2(DXyIF) 2(O2CCH3)2(µ2-O) 2 is presented. We have performed extensive density functional theory (DFT) and complete active space self-consistent field (CASSCF) calculations. For both the full target complex and a model derived by replacing xylyl and methyl groups with hydrogens we observe that the central Mo2(µ 2-O)2 motif displays C2h rather than D 2h symmetry. Analytical CASSCF frequency calculations prove that the rhomboidal distortion of the complex from D2h to C2h is due to a vibronic mixing of the ground electronic state and a low-lying pd* excited state. {\textcopyright} 2009 American Chemical Society.",

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T1 - Theoretical study of the pseudo-jahn-teller effect in the edge-sharing bioctahedral complex Mo2(DXyIF)2(O2CCH 3)2(μ2-O)2

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AU - Paterson, Martin J.

PY - 2009/11/16

Y1 - 2009/11/16

N2 - A study of the D2h to C2h pseudo-Jahn-Teller distortion in the edge-sharing bioctahedral complex Mo2(DXyIF) 2(O2CCH3)2(µ2-O) 2 is presented. We have performed extensive density functional theory (DFT) and complete active space self-consistent field (CASSCF) calculations. For both the full target complex and a model derived by replacing xylyl and methyl groups with hydrogens we observe that the central Mo2(µ 2-O)2 motif displays C2h rather than D 2h symmetry. Analytical CASSCF frequency calculations prove that the rhomboidal distortion of the complex from D2h to C2h is due to a vibronic mixing of the ground electronic state and a low-lying pd* excited state. © 2009 American Chemical Society.

AB - A study of the D2h to C2h pseudo-Jahn-Teller distortion in the edge-sharing bioctahedral complex Mo2(DXyIF) 2(O2CCH3)2(µ2-O) 2 is presented. We have performed extensive density functional theory (DFT) and complete active space self-consistent field (CASSCF) calculations. For both the full target complex and a model derived by replacing xylyl and methyl groups with hydrogens we observe that the central Mo2(µ 2-O)2 motif displays C2h rather than D 2h symmetry. Analytical CASSCF frequency calculations prove that the rhomboidal distortion of the complex from D2h to C2h is due to a vibronic mixing of the ground electronic state and a low-lying pd* excited state. © 2009 American Chemical Society.

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DO - 10.1021/ic901285f

M3 - Article

SN - 0020-1669

VL - 48

SP - 10652

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JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 22

ER -

Theoretical study of the pseudo-jahn-teller effect in the edge-sharing bioctahedral complex Mo2(DXyIF)2(O2CCH 3)2(μ2-O)2

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Theoretical study of the pseudo-jahn-teller effect in the edge-sharing bioctahedral complex Mo₂(DXyIF)₂(O₂CCH ₃)₂(μ₂-O)₂