Correction to Multiconfiguration Pair-Density Functional Theory Outperforms Kohn–Sham Density Functional Theory and Multireference Perturbation Theory for Ground-State and Excited-State Charge Transfer

2015 ◽  
Vol 12 (1) ◽  
pp. 455-455
Author(s):  
Soumen Ghosh ◽  
Andrew L. Sonnenberger ◽  
Chad E. Hoyer ◽  
Donald G. Truhlar ◽  
Laura Gagliardi
Keyword(s):  
Density Functional Theory ◽  
Perturbation Theory ◽  
Excited State ◽  
Charge Transfer ◽  
Ground State ◽  
Density Functional ◽  
Functional Theory ◽  
Multireference Perturbation Theory ◽  
Pair Density ◽  
State Charge

Accurate description of hybridized local and charge-transfer excited-state in donor–acceptor molecules using density functional theory

RSC Advances ◽  
2016 ◽  
Vol 6 (110) ◽  
pp. 108404-108410 ◽  
Author(s):  
Y. Y. Pan ◽  
J. Huang ◽  
Z. M. Wang ◽  
S. T. Zhang ◽  
D. W. Yu ◽  
...  
Keyword(s):  
Density Functional Theory ◽  
Excited State ◽  
Charge Transfer ◽  
Ground State ◽  
Density Functional ◽  
Accurate Description ◽  
Functional Theory ◽  
Donor Acceptor ◽  
Acceptor Molecules

The ωB97X was the most reliable functional for the accurate description of HLCT state at ground state and excited state.

Investigation of Photo-Induced C-H Bond Activating by CpRh(CO)2 Complex Using Density Functional Theory

2011 ◽  
Vol 279 ◽  
pp. 170-173
Author(s):  
Qing Liong Liu ◽  
Shu Wei Wang ◽  
Li Lv ◽  
Xiao Jing Wang
Keyword(s):  
Density Functional Theory ◽  
Excited State ◽  
Charge Transfer ◽  
Transfer Process ◽  
Ground State ◽  
Density Functional ◽  
Light Irradiation ◽  
Functional Theory ◽  
Structural Distortions ◽  
First Excited State

The charge transfer and structural distortions that occurred in the complex CpRh(CO)2 upon excitation with an light irradiation were studied by density functional theory (DFT). The calculations showed that the electrons transferred from Cp to CO ligands with the transition of CpRh(CO)2 from ground state to the first excited state. Accompanying with this transfer process, CpM(CO)2 became distorted and the linear bond of M-CO became bent upon excitation. The second excitation is the strongest excitation which is identified to be metal to ligand CO charge transfer (MLCT) excitations. We also found the lowest excited state has little effect for the M-CO bond photoactivation while the photodissociation of CO from CpM(CO)2 can be achieved in the second excited state.

Multiconfiguration pair-density functional theory for doublet excitation energies and excited state geometries: the excited states of CN

2017 ◽  
Vol 19 (44) ◽  
pp. 30089-30096 ◽  
Author(s):  
Jie J. Bao ◽  
Laura Gagliardi ◽  
Donald G. Truhlar
Keyword(s):  
Density Functional Theory ◽  
Excited State ◽  
Excited States ◽  
Density Functional ◽  
Excitation Energies ◽  
Functional Theory ◽  
Pair Density

MC-PDFT is more accurate than CR-EOM-CCSD(T) or TDDFT when averaged over the first four adiabatic excitation energies of CN.

Ground-state actinide chemistry with scalar-relativistic multiconfiguration pair-density functional theory

2019 ◽  
Vol 151 (13) ◽  
pp. 134102 ◽  
Author(s):  
Olajumoke Adeyiga ◽  
Olabisi Suleiman ◽  
Naveen K. Dandu ◽  
Samuel O. Odoh
Keyword(s):  
Density Functional Theory ◽  
Ground State ◽  
Density Functional ◽  
Functional Theory ◽  
Pair Density ◽  
Actinide Chemistry

A density functional theory and spectroscopic study of intramolecular quenching of metal-to-ligand charge-transfer excited states in some mono-bipyridine ruthenium(II) complexes

2014 ◽  
Vol 92 (10) ◽  
pp. 996-1009 ◽  
Author(s):  
Shivnath Mazumder ◽  
Ryan A. Thomas ◽  
Richard L. Lord ◽  
H. Bernhard Schlegel ◽  
John F. Endicott
Keyword(s):  
Density Functional Theory ◽  
Excited State ◽  
Charge Transfer ◽  
Excited States ◽  
Lower Energy ◽  
Density Functional ◽  
Dimethyl Sulfide ◽  
Intramolecular Electron Transfer ◽  
Functional Theory ◽  
Ligand Charge Transfer

The complexes [Ru(NCCH3)4bpy]2+ and [Ru([14]aneS4)bpy]2+ ([14]aneS4 = 1,4,8,11-tetrathiacyclotetradecane, bpy = 2,2′-bipyridine) have similar absorption and emission spectra but the 77 K metal-to-ligand charge-transfer (MLCT) excited state emission lifetime of the latter is less than 0.3% that of the former. Density functional theory modeling of the lowest energy triplet excited states indicates that triplet metal centered (3MC) excited states are about 3500 cm−1 lower in energy than their 3MLCT excited states in both complexes. The differences in excited state lifetimes arise from a much larger coordination sphere distortion for [Ru(NCCH3)4bpy]2+ and the associated larger reorganizational barrier for intramolecular electron transfer. The smaller ruthenium ligand distortions of the [Ru([14]aneS4)bpy]2+ complex are apparently a consequence of stereochemical constraints imposed by the macrocyclic [14]aneS4 ligand, and the 3MC excited state calculated for the unconstrained [Ru(S(CH3)2)4bpy]2+ complex (S(CH3)2 = dimethyl sulfide) is distorted in a manner similar to that of [Ru(NCCH3)4bpy]2+. Despite the lower energy calculated for its 3MC than 3MLCT excited state, [Ru(NCCH3)4bpy]2+ emits strongly in 77 K glasses with an emission quantum yield of 0.47. The emission is biphasic with about a 1 μs lifetime for its dominant (86%) emission component. The 405 nm excitation used in these studies results in a significant amount of photodecomposition in the 77 K glasses. This is a temperature-dependent biphotonic process that most likely involves the bipyridine-radical anionic moiety of the 3MLCT excited state. A smaller than expected value found for the radiative rate constant is consistent with a lower energy 3MC than 3MLCT state.

Binding Energies of Organic Charge-Transfer Complexes Calculated by First-Principles Methods

1998 ◽  
Vol 63 (8) ◽  
pp. 1223-1244 ◽  
Author(s):  
Cordula Rauwolf ◽  
Achim Mehlhorn ◽  
Jürgen Fabian
Keyword(s):  
Density Functional Theory ◽  
Charge Transfer ◽  
Ground State ◽  
Density Functional ◽  
Binding Energies ◽  
Basis Set ◽  
Dispersion Energy ◽  
Functional Theory ◽  
Basis Set Superposition Error ◽  
Donor And Acceptor

Weak interactions between organic donor and acceptor molecules resulting in cofacially-stacked aggregates ("CT complexes") were studied by second-order many-body perturbation theory (MP2) and by gradient-corrected hybrid Hartree-Fock/density functional theory (B3LYP exchange-correlation functional). The complexes consist of tetrathiafulvalene (TTF) and related compounds and tetracyanoethylene (TCNE). Density functional theory (DFT) and MP2 molecular equilibrium geometries of the component structures are calculated by means of 6-31G*, 6-31G*(0.25), 6-31++G**, 6-31++G(3df,2p) and 6-311G** basis sets. Reliable molecular geometries are obtained for the donor and acceptor compounds considered. The geometries of the compounds were kept frozen in optimizing aggregate structures with respect to the intermolecular distance. The basis set superposition error (BSSE) was considered (counterpoise correction). According to the DFT and MP2 calculations laterally-displaced stacks are more stable than vertical stacks. The charge transfer from the donor to the acceptor is small in the ground state of the isolated complexes. The cp-corrected binding energies of TTF/TCNE amount to -1.7 and -6.3 kcal/mol at the DFT(B3LYP) and MP2(frozen) level of theory, respectively (6-31G* basis set). Larger binding energies were obtained by Hobza's 6-31G*(0.25) basis set. The larger MP2 binding energies suggest that the dispersion energy is underestimated or not considered by the B3LYP functional. The energy increases when S in TTF/TCNE is replaced by O or NH but decreases with substitution by Se. The charge-transferred complexes in the triplet state are favored in the vertical arrangement. Self-consistent-reaction-field (SCRF) calculations predicted a gain in binding energy with solvation for the ground-state complex. The ground-state charge transfer between the components is increased up to 0.8 e in polar solvents.

Tunable spectra and charge transfer process of benzodifurandione-based polymer by sulfur substitution

RSC Advances ◽  
2015 ◽  
Vol 5 (24) ◽  
pp. 18492-18500 ◽  
Author(s):  
Chaofan Sun ◽  
Dawei Qi ◽  
Yuanzuo Li ◽  
LinPo Yang
Keyword(s):  
Density Functional Theory ◽  
Charge Transfer ◽  
Charge Transport ◽  
Transport Properties ◽  
Transfer Process ◽  
Ground State ◽  
Density Functional ◽  
Charge Transfer Process ◽  
Functional Theory ◽  
Ground State Geometry

The ground state geometry, optical and charge transport properties of benzodifurandione-based PPV (BDPPV) have been studied with density functional theory methods.

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