Systematic ab initio study of the ligand field spectra of hexacyanometalate complexes

Pierloot, Kristine; Praet, E Van; Vanquickenborne, L. G.; Roos, BO

doi:10.1021/j100149a021

Cited by 68 publications

(94 citation statements)

References 7 publications

(7 reference statements)

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“…The second and third columns of this table contain the results of the calculations performed with the effective core description for the two molybdenum centers. The excitation energies for the minimal (6, 10) active space (4d orbitals of Mo) and the larger (12,15) active space can be found in the second and third column, respectively. The fourth and fifth columns of the same table contain the results obtained for the same active spaces in combination with the all-electron basis set.…”

Section: Resultsmentioning

confidence: 99%

“…10 9,[12][13][14] The calculations on compounds II and III have been performed by employing a minimal active space for the expansion of the zeroth-order CASSCF wave function. It comprises the five 4d molybdenum orbitals among which the three valence electrons are distributed: CAS (3,5).…”

Section: Computational Detailsmentioning

confidence: 99%

“…The second one is an extended active space that also includes along with the minimal active space the 5s, π, and π* orbitals of the bridging cyanide ligand and its six valence electrons. This second active space can therefore be abbreviated as CAS (12,15). At the CASPT2 level, the dynamic correlation was calculated by including all the molecular orbitals of the complexes originating from all the valence atomic orbitals, i.e., the 2s and 2p orbitals of the carbon and nitrogen atoms and the 4p and 4d orbitals of molybdenum.…”

Section: Computational Detailsmentioning

confidence: 99%

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[Mo₂(CN)₁₁]:^5- A Detailed Description of Ligand-Field Spectra and Magnetic Properties by First-Principles Calculations

et al. 2005

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An ab initio multiconfigurational approach has been used to calculate the ligand-field spectrum and magnetic properties of the title cyano-bridged dinuclear molybdenum complex. The rather large magnetic coupling parameter J for a single cyano bridge, as derived experimentally for this complex by susceptibility measurements, is confirmed to a high degree of accuracy by our CASPT2 calculations. Its electronic structure is rationalized in terms of spin-spin coupling between the two constituent hexacyano-monomolybdate complexes. An in-depth analysis on the basis of Anderson's kinetic exchange theory provides a qualitative picture of the calculated CASSCF antiferromagnetic ground-state eigenvector in the Mo dimer. Dynamic electron correlations as incorporated into our first-principles calculations by means of the CASPT2 method are essential to obtain quantitative agreement between theory and experiment.

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Section: Resultsmentioning

confidence: 99%

Section: Computational Detailsmentioning

confidence: 99%

Section: Computational Detailsmentioning

confidence: 99%

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[Mo₂(CN)₁₁]:^5- A Detailed Description of Ligand-Field Spectra and Magnetic Properties by First-Principles Calculations

et al. 2005

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“…Considering the wide successful results obtained with ab initio methods in organic and inorganic compounds and the great controlability offered by this method is surprising how simply these results were discarded. Indeed many authors have been carring out HF/CI calculations on several metal transition compounds claiming an error smaller 21,22 than 0.5 eV to the experimental energies. The goal of this work, considering our limited computational resources, is to present simple, economical and balanced HF/CI-SD calculations designed to establish the correct qualitative orbital picture.…”

Section: For Complexes Of the Type [M(cn)5no] -2mentioning

confidence: 99%

A HF/CI-SD study of the low-lying states of nitroprusside ion

Hollauer¹,

Olabe²

1997

J. Braz. Chem. Soc.

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Desde a descoberta de dois estado meta-estáveis gerados por excitação ótica do nitroprussiato de sódio cristalino, Na2[Fe(CN)5NO].2H2O (SNP), exibindo longa meia-vida a temperaturas abaixo de 160 K, grande esforço vem sendo realizado no sentido de entender a estrutura eletrônica de sistemas correlatos. Apesar deste esforço, a natureza dos orbitais de fronteira e dos processos de excitação eletrônica de baixa energia são, ainda hoje, controversos. Cálculos iniciais EHT mostram que o HOMO possuia caráter do orbital 3d metálico, enquanto o LUMO possuia uma contribuição dominantemente π* (NO). Entretanto, cálculos INDO definiram o orbital metálido d como orbital de valência interna com vários elétron-volts em energia de Koopmans. O espectro vertical foi estimado através de cálculos HF/Cl-SD com bases de qualidade double-zeta e potenciais de caroço. As energias de Koopmans para os resultados ab initio estão de acordo com os resultados de Bottomley e Grein, e atribuem as primeiras excitações a processos de transferência de carga (TC) do trans-cyano para os ligantes nitrosila. Forças de oscilador foram calculadas e os resultados mostraram intensidades comparáveis com os resultados experimentais. A energia de excitação para o processo de transferência de carga metal → NO, 8e → 13e (dxz,dyz → π* NO) foi estimada em 4.52 eV e exibindo intensa banda de absorção. A segunda excitação de transferência de carga, 1b 2 → 13e (dxy → π* NO), apontada por trabalhos prévios como uma típica banda de transferência de carga (TC) mostra uma pequena intensidade em 5.04 eV. Nos cálculos foi observado que o ordenamento SCF é muito independente do conjunto de base utilizado para o metal. Bases metálicas de caráter mínimo mostram resultados em grande concordância com os resultados EHT, enquanto as bases double-zeta empurram os orbitais d metálicos para os orbitais de valência interna. O ordenamento das energias HF foi empregado no sentido de interpretar resultados de experimentos fotoquímicos e de termoanálise do SNP e os resultados parecem mostrar boa concordância com as propriedades calculadas.Since the discovering of two photoexcited metastable states of crystalline sodium nitroprusside, Na2[Fe(CN)5NO].2H2O (SNP), showing rather long lifetimes at temperatures below 160 K, much effort has been devoted toward the study of its electronic structure. Despite this tremendous effort the nature of the frontier orbitals and the related low energy excitations remains controversial. Early calculations, EHT, showed the HOMO as mainly the metallic 3d orbital while the LUMO had a major π* (NO) contribution. However INDO calculations, clearly set the metal d orbital many electron-volts deep in core. The vertical electronic spectrum have been estimated through ab initio HF/CI-SD with a double-zeta quality basis set. The ab initio results support Bottomley and Grein's interpretations and assign the first electronic transitions to ligand-to-ligand charge-transfer excitation from trans-cyano to nitrosyl ligands. The corresponding oscillator strengths have b...

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“…21 Since this time, perturbation theory methods built on a multireference zeroth-order wave function have been used to examine the magnetic coupling in a variety of metal complexes and materials. [22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37][38][39][40] Other theoretical methods for calculating the magnetic coupling for biradicals and binuclear complexes have been discussed recently. 41 Ab initio calculations can provide new insights into the interactions between metal centers and ligands.…”

Section: Introductionmentioning

confidence: 99%

Influence of Multi-atom Bridging Ligands on the Electronic Structure and Magnetic Properties of Homodinuclear Titanium Molecules

Aikens

Gordon

2005

J. Phys. Chem. A

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The electronic structure and magnetic properties of homodinuclear titanium(III) molecules with bridging ligands from groups 14, 15, and 16 are examined. Single-and multireference methods with triple-ζ plus polarization basis sets are employed. Dynamic electron correlation effects are included via second-order multireference perturbation theory. Isotropic interaction parameters are calculated, and two of the complexes studied are predicted to be ferromagnetic based on multireference second-order perturbation (MRMP2) theory, using the TZVP(fg) basis set. Zero-field splitting parameters are determined using spin−orbit coupling obtained from complete active space (CAS) self-consistent field (SCF) and multiconfigurational quasidegenerate perturbation theory (MCQDPT) wave functions. Three Breit−Pauli-based spin coupling methods were employed: full Breit−Pauli (HSO2), the partial two-electron method (P2E), and the semiempirical oneelectron method (HSO1). Disciplines Chemistry CommentsReprinted (adapted) The electronic structure and magnetic properties of homodinuclear titanium(III) molecules with bridging ligands from groups 14, 15, and 16 are examined. Single-and multireference methods with triple-plus polarization basis sets are employed. Dynamic electron correlation effects are included via second-order multireference perturbation theory. Isotropic interaction parameters are calculated, and two of the complexes studied are predicted to be ferromagnetic based on multireference second-order perturbation (MRMP2) theory, using the TZVP(fg) basis set. Zero-field splitting parameters are determined using spin-orbit coupling obtained from complete active space (CAS) self-consistent field (SCF) and multiconfigurational quasi-degenerate perturbation theory (MCQDPT) wave functions. Three Breit-Pauli-based spin coupling methods were employed: full Breit-Pauli (HSO2), the partial two-electron method (P2E), and the semiempirical one-electron method (HSO1).

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Systematic ab initio study of the ligand field spectra of hexacyanometalate complexes

Cited by 68 publications

References 7 publications

[Mo₂(CN)₁₁]:^5- A Detailed Description of Ligand-Field Spectra and Magnetic Properties by First-Principles Calculations

[Mo₂(CN)₁₁]:^5- A Detailed Description of Ligand-Field Spectra and Magnetic Properties by First-Principles Calculations

A HF/CI-SD study of the low-lying states of nitroprusside ion

Influence of Multi-atom Bridging Ligands on the Electronic Structure and Magnetic Properties of Homodinuclear Titanium Molecules

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Systematic ab initio study of the ligand field spectra of hexacyanometalate complexes

Cited by 68 publications

References 7 publications

[Mo2(CN)11]:5- A Detailed Description of Ligand-Field Spectra and Magnetic Properties by First-Principles Calculations

[Mo2(CN)11]:5- A Detailed Description of Ligand-Field Spectra and Magnetic Properties by First-Principles Calculations

A HF/CI-SD study of the low-lying states of nitroprusside ion

Influence of Multi-atom Bridging Ligands on the Electronic Structure and Magnetic Properties of Homodinuclear Titanium Molecules

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[Mo₂(CN)₁₁]:^5- A Detailed Description of Ligand-Field Spectra and Magnetic Properties by First-Principles Calculations

[Mo₂(CN)₁₁]:^5- A Detailed Description of Ligand-Field Spectra and Magnetic Properties by First-Principles Calculations