SARACEN ? molecular structures from theory and experiment: the best of both worlds

Mitzel, Norbert W.; Rankin, David W. H.

doi:10.1039/b307022k

Cited by 132 publications

(113 citation statements)

References 47 publications

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“…1 Secondly, they provide key 20 reference data for assessment of computational methods aspiring to understand and predict this chemistry. Such validation is particularly dearly needed in the blooming field of density functional theory (DFT), where the success or failure of a particular exchange-correlation functional is hard 25 to predict beforehand.…”

Section: Introductionmentioning

confidence: 99%

Electric field gradients of transition metal complexes from density functional theory: assessment of functionals, geometries and basis sets

Björnsson

Bühl

2010

Dalton Trans.

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Electric field gradients (EFGs) were computed for the first-row transition metal nuclei in Cr(C 6 H 6 )(CO) 3 , MnO 3 F, Mn(CO) 5 H, MnCp(CO) 3 , Co(CO) 4 H, Co(CO) 3 (NO) and VCp(CO) 4 , for which experimental gas-phase data (in form of nuclear quadrupole coupling constants) are available from microwave spectroscopy. A variety of exchange-correlation functionals were assessed, 10 among which range-separated hybrids (such as CAM-B3LYP or LC-ωPBE) perform best, followed by global hybrids (such as B3LYP) and gradient-corrected functionals (such as BP86). While large basis sets are required on the metal atom for converged EFGs, smaller basis sets can be employed on the ligands. In most cases, EFGs show little sensitivity toward the geometrical parameters.

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Section: Introductionmentioning

confidence: 99%

Electric field gradients of transition metal complexes from density functional theory: assessment of functionals, geometries and basis sets

Björnsson

Bühl

2010

Dalton Trans.

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“…The SARACEN [58][59][60] method was used for the refinement of experimental data, with the required restraints based upon comparison of calculations at the MP2, B3LYP, and M06-2X levels of theory, and with 6-31G(d) and aug-cc-pVDZ basis sets (using aug-cc-pVDZ-PP as a pseudopotential for Br in 4). Vibrational corrections were based upon data from SHRINK [51,52], calculated using force constants obtained from GAUSSIAN. As is common, because they are not particularly well defined from the GED data, restraints were placed upon the distance difference parameters, as well as parameters associated with hydrogen atoms.…”

Section: Ged Studiesmentioning

confidence: 99%

Structures of Tetrasilylmethane Derivatives (XMe₂Si)₂C(SiMe₃)₂ (X = H, Cl, Br) in the Gas Phase, and their Dynamic Structures in Solution

et al. 2015

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Article:Wann, Derek A. orcid.org/0000-0002-5495-274X, Robinson, Matthew S., Bätz, Karin et al. eprints@whiterose.ac.uk https://eprints.whiterose.ac.uk/ Reuse Unless indicated otherwise, fulltext items are protected by copyright with all rights reserved. The copyright exception in section 29 of the Copyright, Designs and Patents Act 1988 allows the making of a single copy solely for the purpose of non-commercial research or private study within the limits of fair dealing. The publisher or other rights-holder may allow further reproduction and re-use of this version -refer to the White Rose Research Online record for this item. Where records identify the publisher as the copyright holder, users can verify any specific terms of use on the publisher's website. TakedownIf you consider content in White Rose Research Online to be in breach of UK law, please notify us by emailing eprints@whiterose.ac.uk including the URL of the record and the reason for the withdrawal request. The structures of the molecules C(SiXMe 2 ) 4 (X = H, F, Cl, Br) have been determined by gas electron diffraction (GED). Ab initio calculations revealed nine potential minima for each species, with significant ranges of energies. For the H, F, Cl, and Br derivatives nine, seven, two, and two conformers were modelled, respectively, as they were quantum-chemically predicted to be present in measurable quantities. Variable-temperature 1 H and 29 Si solutionphase NMR studies and, where applicable, 13 C NMR, 1 H/ 29 Si NMR shift-correlation, and 1 H NMR saturation-transfer experiments are reported for C(SiXMe 2 ) 4 (X = H, Cl, Br, and also I).At low temperature in solution two conformers (one C 1 -symmetric and one C 2 -symmetric) are observed for each of C(SiXMe 2 ) 4 (X = Cl, Br, I), in agreement with the isolated molecule ab initio calculations carried out as part of this work for X = Cl, Br. C(SiHMe 2 ) 4 is present as a single C 1 -symmetric conformer in solution at the temperatures at which the NMR experiments were performed.

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“…17,18 All independent geometric parameters were refined using a least-squares method and restraints were applied, using the SARACEN method, [5][6][7] to five parameters that could otherwise not be refined (Table 4). The restraints were based on values calculated at the MP2/6-311++G** level.…”

Section: Gas Electron Diffraction (Ged)mentioning

confidence: 99%

“…[5][6][7] The structure of 1,2-ditert-butyldisilane 1 was found to be anti with C 2 symmetry at room temperature, while 1,2-ditert-butyltetrachlorodisilane 2 returned a transoid conformation by both GED and ab initio methods. Both of these systems displayed evidence of steric crowding, with larger than average bond angles observed about the silicon atoms.…”

Section: Introductionmentioning

confidence: 99%

Molecular Structure of 1,2-Bis(trifluoromethyl)-1,1,2,2-tetramethyldisilane in the Gas, Liquid, and Solid Phases: Unusual Conformational Changes between Phases

et al. 2014

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The molecular structure of 1,2-bis(trifluoromethyl)-1,1,2,2-tetramethyldisilane has been determined in three different phases (solid, liquid and gas) using various spectroscopic and diffraction techniques. Both the solid-state and gas-phase investigations revealed only one conformer to be present in the sample analyzed, while the liquid phase revealed the presence of three conformers. The data have been reproduced using computational methods and a rationale is presented for the observation of three conformers in the liquid state.

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SARACEN ? molecular structures from theory and experiment: the best of both worlds

Cited by 132 publications

References 47 publications

Electric field gradients of transition metal complexes from density functional theory: assessment of functionals, geometries and basis sets

Electric field gradients of transition metal complexes from density functional theory: assessment of functionals, geometries and basis sets

Structures of Tetrasilylmethane Derivatives (XMe₂Si)₂C(SiMe₃)₂ (X = H, Cl, Br) in the Gas Phase, and their Dynamic Structures in Solution

Molecular Structure of 1,2-Bis(trifluoromethyl)-1,1,2,2-tetramethyldisilane in the Gas, Liquid, and Solid Phases: Unusual Conformational Changes between Phases

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SARACEN ? molecular structures from theory and experiment: the best of both worlds

Cited by 132 publications

References 47 publications

Electric field gradients of transition metal complexes from density functional theory: assessment of functionals, geometries and basis sets

Electric field gradients of transition metal complexes from density functional theory: assessment of functionals, geometries and basis sets

Structures of Tetrasilylmethane Derivatives (XMe2Si)2C(SiMe3)2 (X = H, Cl, Br) in the Gas Phase, and their Dynamic Structures in Solution

Molecular Structure of 1,2-Bis(trifluoromethyl)-1,1,2,2-tetramethyldisilane in the Gas, Liquid, and Solid Phases: Unusual Conformational Changes between Phases

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Structures of Tetrasilylmethane Derivatives (XMe₂Si)₂C(SiMe₃)₂ (X = H, Cl, Br) in the Gas Phase, and their Dynamic Structures in Solution