Article

1999 ◽  
Vol 77 (1) ◽  
pp. 16-23
Author(s):  
Pierre D Harvey ◽  
Christian Reber
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Luminescence Spectra ◽  
Functional Theory ◽  
Square Planar ◽  
Orbital Excitation ◽  
Halide Complexes ◽  
Spin Triplet ◽  
Length Changes ◽  
Calculated Bond Length

Density functional theory is used to characterize the lowest energy excited spin triplet orbital configurations of square-planar halide complexes of palladium(II). Calculations for the eg –> b1g orbital excitation (D4h labels) predict a non-totally symmetric distortion along the b1g normal coordinate, leading to unequal bond lengths for perpendicular metal-ligand bonds (D2h symmetry). Calculated bond length changes are 0.15 Å (0.11 Å) and 0.05 Å (0.00 Å) for PdCl42- (PdBr42-). These values compare favorably to the emitting-state distortions of 0.12 Å and 0.09 Å for K2PdCl4 (0.12 Å, and 0.07 Å for K2PdBr4) determined from resolved single-crystal luminescence spectra. The calculations indicate that the non-totally symmetric distortion is an intrinsic molecular property of these complexes.Key words: palladium(II) complexes, excited state distortions, density functional theory.

CO2 reduction catalysis by tunable square-planar transition-metal complexes: a theoretical investigation using nitrogen-substituted carbon nanotube models

2017 ◽  
Vol 19 (43) ◽  
pp. 29068-29076 ◽  
Author(s):  
Yu-Te Chan ◽  
Ming-Kang Tsai
Keyword(s):  
Density Functional Theory ◽  
Carbon Nanotube ◽  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Density Functional ◽  
Co2 Reduction ◽  
Functional Theory ◽  
Square Planar ◽  
Planar Transition

The CO2 reduction capabilities of transition-metal-chelated nitrogen-substituted carbon nanotube models (TM-4N2v-CNT, TM = Fe, Ru, Os, Co, Rh, Ir, Ni, Pt or Cu) are characterized by density functional theory.

DFT STUDIES ON THE STABILITY OF THE TRANS AND CIS ISOMERS IN THE SQUARE PLANAR PALLADIUM(II) COMPLEXES Pd(I)(PPh3)(η3-XCHC(Ph)CHR) (X = CMe3, CO2Me, P(O)(OMe)2, AND SO2H; R = H, Me)

2008 ◽  
Vol 07 (04) ◽  
pp. 505-515
Author(s):  
LIQIN XUE ◽  
GUOCHEN JIA ◽  
ZHENYANG LIN
Keyword(s):  
Density Functional Theory ◽  
Electronic Properties ◽  
Relative Stability ◽  
Density Functional ◽  
Density Functional Theory Calculations ◽  
Dft Studies ◽  
Functional Theory ◽  
Square Planar ◽  
The Stability ◽  
Cis Isomer

The relative stability of the trans and cis isomers in the square planar palladium(II) complexes Pd ( I )( PPh 3)(η3- XCHC ( Ph ) CHR ) ( X = H , Me , CMe 3, CO 2 Me , P ( O )( OMe )2, and SO 2 H ; R = H , Me ) was investigated with the aid of the B3LYP density functional theory calculations. We examined how the substituents X, with different electronic properties, of the η3-allyl ligands affect the relative stability of the trans and cis isomers. Through the investigation, we were able to explain the trans/cis relative stability derived from the experimentally measured trans/cis isomer ratios in the palladium(II) complexes.

scholarly journals Computational studies of Ni(II) photosensitizers complexes containing 1,1′-bis(diphenylphosphino)ferrocene and dithio ligands

2020 ◽  
Vol 98 (4) ◽  
pp. 194-203 ◽  
Author(s):  
Sefia Brahim ◽  
Houari Brahim ◽  
Stéphane Humbel ◽  
Ali Rahmouni
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Dye Sensitized Solar Cells ◽  
Substituent Effects ◽  
Spectroscopic Properties ◽  
Basis Sets ◽  
Functional Theory ◽  
Square Planar ◽  
Td Dft ◽  
Sensitized Solar Cells

Detailed theoretical studies of Ni(II) complexes in a distorted square planar form and containing dithio and (P, P) chelating ligands were performed. These Ni(II) complexes are investigated for their use in dye-sensitized solar cells (DSSC). Structures and UV–vis spectra are calculated at density functional theory (DFT) and time-dependent density functional theory (TD-DFT) theories using B3LYP and CAM-B3LYP functionals and 6-31G(d,p) and 6-31G+(d) basis sets. Geometry optimizations result in excellent agreement with the experimental results. Moreover, the analysis of the frontier molecular orbitals (FMOs) allowed a detailed assignment and a clear analysis of the electronic transitions. The TD-DFT calculations reproduce the main spectroscopic properties observed and substituent effects. The results reveal that all absorption spectra are characterized by mixed character mainly dominated by metal to ligand and ligand to ligand charge transfers (MLCT and LLCT). We unveil how the substituent variations affect the DSSCs features of the complexes.

Hexafluorophosphates of chlorotris(dimethyl sulfide)platinum(II) and bromotris(dimethyl sulfide)platinum(II)

2003 ◽  
Vol 59 (11) ◽  
pp. m432-m434
Author(s):  
Christian Hansson ◽  
Vadim Yu. Kukushkin ◽  
Karin Lövqvist ◽  
Shen Yong ◽  
Åke Oskarsson
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Dimethyl Sulfide ◽  
Weak Interactions ◽  
Density Functional Theory Calculations ◽  
The Other ◽  
Functional Theory ◽  
The Third ◽  
Square Planar ◽  
Coordination Plane

The title compounds, chlorotris(dimethyl sulfide-κS)platinum(II) hexafluorophosphate, [PtCl(C2H6S)3]PF6, and bromotris(dimethyl sulfide-κS)platinum(II) hexafluorophosphate, [PtBr(C2H6S)3]PF6, are isomorphous and are composed of [PtX(dms)3]+ complex cations (X = Cl and Br, and dms is dimethyl sulfide) and PF6 − anions. The Pt atom is coordinated by three S atoms and one X atom in a pseudo-square-planar coordination, with Pt—S distances in the range 2.293 (1)–2.319 (2) Å. Two dms ligands have a staggered conformation with respect to the coordination plane, while the third is rotated by ∼90° compared with the orientation of the other two. The packing can be described as consisting of [PtX(dms)3]2(PF6)2 units with a centre of symmetry. In this description, the PtII atom has a pseudo-octahedral coordination, with four normal bonds and two long weak interactions. Density-functional theory calculations show that a conformation in which one dms ligand is not staggered is less favourable than having all three dms ligands staggered.

Bareversusprotected tetrairidium clusters by density functional theory

2018 ◽  
Vol 20 (46) ◽  
pp. 29480-29492 ◽  
Author(s):  
Maurício J. Piotrowski ◽  
Glaucio R. Nagurniak ◽  
Eder H. da Silva ◽  
Renato L. T. Parreira
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Functional Theory ◽  
Tetrahedral Configuration ◽  
Square Planar

The lowest energy configuration of the tetrairidium cluster is a square planar isomer in bare case, while the tetrahedral configuration is assumed in different chemical environments.

scholarly journals PENENTUAN GEOMETRI DAN KARAKTERISTIK IKATAN SENYAWA KOMPLEKS NI(II)-DIBUTILDITIOKARBAMAT DENGAN METODE DENSITY FUNCTIONAL THEORY

2017 ◽  
Vol 7 (2) ◽  
Author(s):  
Nicolin Tirza Pongajow ◽  
Juliandri Juliandri ◽  
Iwan Hastiawan
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Nbo Analysis ◽  
Computational Method ◽  
Basis Set ◽  
Planar Geometry ◽  
Chemical Calculation ◽  
Functional Theory ◽  
Square Planar ◽  
Electron Contribution

AbstrakDensity Functional Theory (DFT) merupakan salah satu metode komputasi yang digunakan untuk perhitungan kimia. Metode ini dapat menyelesaian persamaan Schrödinger secara sederhana karena didasarkan pada densitas elektron. Dalam penelitian ini ditentukan geometri dan karaktersitik ikatan dari senyawa kompleks Ni(II)-dibutilditiokarbamat menggunakan metode DFT dengan fungsi B3LYP, B3PW91 dan BLYP. Basis set yang akan digunakan adalah LANL2DZ dan perangkat lunak Gaussian 03W. Hasil optimasi geometri Ni(II)-dibutilditiokarbamat menunjukkan bentuk struktur yang sama dengan Ni(II)-dietilditiokarbamat sebagai data pembanding, yaitu persegi planar. Keterisian elektron pada ikatan Ni – S adalah 1,8873 elektron, yang merupakan 20,24 % elektron dari Ni dan 79,76 % dari S. Bentuk geometri persergi planar dibuktikan dengan hasil analisis NBO yang menunjukkan hibridisasi Ni(II)-dibutilditiokarbamat adalah d1,05sp2.05. Kata kunci: DFT, dibutilditiokarbamat, geometri, karakteristik ikatan, senyawa kompleks. AbstractDensity Functional Theory (DFT) is one of computational method that used for chemical calculation. This method simplifies the complex solution of Schrödinger equation using electron density. In this study the geometry and bond characterization of Ni(II)-dibutyldithiocarbamat complex compound was determined. The computational method used was Density Functional Theory as applied in B3LYP, B3PW91 and BLYP functions. All calculations were performed at LANL2DZ level of basis set as implemented Gaussian 03W. The theoretical result on geometry showed a similar structure to square-planar Ni(II)-dietyldithiocarbamate. The electronic occupation of Ni–S molecular orbital was 1.8873 electron, which was 20.24% electron contribution from Ni and 79.76% from S. Square-planar geometry proved by NBO analysis result that the hybridization of Ni(II)-dibutyldithiocarbamate was d1,05sp2.05. Keywords: DFT, dibutyldithiocarbamate, geometry, bond characterization, complexes compound.

MoS2 supported single platinum atoms and their superior catalytic activity for CO oxidation: a density functional theory study

2015 ◽  
Vol 3 (46) ◽  
pp. 23113-23119 ◽  
Author(s):  
Chunmiao Du ◽  
Haiping Lin ◽  
Bin Lin ◽  
Zeyao Ma ◽  
Tingjun Hou ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Catalytic Activity ◽  
Co Oxidation ◽  
Density Functional ◽  
Platinum Atom ◽  
Density Functional Theory Study ◽  
Functional Theory ◽  
Square Planar

The formation of a square-planar 16-electron complex during CO oxidation on a MoS2 supported single platinum atom catalyst.

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