Benchmark Study on Phosphorescence Energies of Anthraquinone Compounds: Comparison between TDDFT and UDFT

Phosphorescent material is widely used in light-emitting devices and in the monitoring of cell phenomena. Anthraquinone compounds (AQs), as important phosphorescent materials, have potential applications as emitters for highly efficient organic light-emitting diodes (OLEDs). Therefore, the accurate calculation of the phosphorescence energy of anthraquinone compounds is particularly important. This study mainly analyzes the phosphorescence energy calculation method of anthraquinone compounds. The time-dependent density functional theory (TDDFT) and the unrestricted density functional theory (UDFT) with seven functionals are selected to calculate the phosphorescence of AQs, taking the high-precision coupled-cluster singles and doubles (CC2) method as a reference. The results showed that the mean unsigned error (MUE) of UDFT was 0.14 eV, which was much smaller than that of TDDFT at 0.29 eV. Therefore, UDFT was more suitable for calculating the phosphorescence energy of AQs. The results obtained by different functionals indicate that the minimum MUE obtained by M06-2X was 0.14 eV. More importantly, the diffuse function in the basis set played an important role in calculating the phosphorescence energy in the M06-HF functional. In the BDBT, FBDBT, and BrBDBT, when M06-HF selected the basis set containing a diffuse function, the differences with CC2 was 0.02 eV, which is much smaller than the one obtained without a diffuse function at 0.80 eV. These findings might be of great significance for the future study of the phosphorescence energy of organic molecules.

[1]  A. A. Braga,et al.  A theoretical approach towards designing of banana shaped non-fullerene chromophores using efficient acceptors moieties: exploration of their NLO response properties , 2023, Optical and Quantum Electronics.

[2]  M. Kaupp,et al.  Reliable TDDFT Protocol Based on a Local Hybrid Functional for the Prediction of Vibronic Phosphorescence Spectra Applied to Tris(2,2'-bipyridine)-Metal Complexes. , 2021, The journal of physical chemistry. A.

[3]  Xia Feng,et al.  Unveiling the theoretical mechanism of purely organic room temperature phosphorescence emission and heteroatomic effects on singlet-triplet intersystem crossing for isopropylthioxanthone derivatives , 2021 .

[4]  Seunghoon Lee,et al.  Optimization of Three State Conical Intersections by Adaptive Penalty Function Algorithm in Connection with the Mixed-Reference Spin-Flip Time-Dependent Density Functional Theory Method (MRSF-TDDFT). , 2021, The journal of physical chemistry. A.

[5]  Aakash D. Nidhankar,et al.  Aggregation-induced phosphorescence of an anthraquinone based emitter. , 2021, Organic & biomolecular chemistry.

[6]  C. Latouche,et al.  DFT vs. TDDFT vs. TDA to simulate phosphorescence spectra of Pt- and Ir-based complexes. , 2020, Dalton transactions.

[7]  B. Tang,et al.  Room-temperature phosphorescence from organic aggregates , 2020, Nature Reviews Materials.

[8]  Guntram Rauhut,et al.  The Molpro quantum chemistry package. , 2020, The Journal of chemical physics.

[9]  A. Al‐Sehemi,et al.  Synthesis, crystal structure, spectroscopic, electronic and nonlinear optical properties of potent thiazole based derivatives: Joint experimental and computational insight , 2020, Journal of Molecular Structure.

[10]  R. Pal,et al.  π-Expanded Thioxanthones - Engineering the Triplet Level of Thioxanthone Sensitizers for Lanthanide-Based Luminescent Probes with Visible Excitation. , 2019, ChemPlusChem.

[11]  A. Hussain,et al.  Electron Donor and Acceptor Influence on the Nonlinear Optical Response of Diacetylene-Functionalized Organic Materials (DFOMs): Density Functional Theory Calculations , 2019, Molecules.

[12]  Kenry,et al.  Enhancing the performance of pure organic room-temperature phosphorescent luminophores , 2019, Nature Communications.

[13]  F. Neese,et al.  Predicting Phosphorescence Rates of Light Organic Molecules Using Time-Dependent Density Functional Theory and the Path Integral Approach to Dynamics , 2019, Journal of chemical theory and computation.

[14]  Andreas Hansen,et al.  A look at the density functional theory zoo with the advanced GMTKN55 database for general main group thermochemistry, kinetics and noncovalent interactions. , 2017, Physical chemistry chemical physics : PCCP.

[15]  B. Tang,et al.  White light emission from a single organic molecule with dual phosphorescence at room temperature , 2017, Nature Communications.

[16]  M. Head‐Gordon,et al.  Thirty years of density functional theory in computational chemistry: an overview and extensive assessment of 200 density functionals , 2017 .

[17]  H. Ågren,et al.  Theory and Calculation of the Phosphorescence Phenomenon. , 2017, Chemical reviews.

[18]  S. Jockusch,et al.  Thioxanthone-benzothiophenes as photoinitiator for free radical polymerization , 2016 .

[19]  Shaohong L Li,et al.  Perspective: Kohn-Sham density functional theory descending a staircase. , 2016, The Journal of chemical physics.

[20]  Wenjian Liu,et al.  Critical Assessment of Time-Dependent Density Functional Theory for Excited States of Open-Shell Systems: II. Doublet-Quartet Transitions. , 2016, Journal of chemical theory and computation.

[21]  Handong Sun,et al.  Enhancing Organic Phosphorescence by Manipulating Heavy-Atom Interaction , 2016 .

[22]  T. Niehaus,et al.  Charge-transfer excited states in phosphorescent organo-transition metal compounds: a difficult case for time dependent density functional theory? , 2015 .

[23]  P. Thilagar,et al.  Recent advances in purely organic phosphorescent materials. , 2015, Chemical communications.

[24]  M. Kasha,et al.  On the Dual Phosphorescence of Xanthone and Chromone in Glassy Hydrocarbon Hosts , 2015, Photochemistry and photobiology.

[25]  Masahiro Ehara,et al.  Benchmark Study on the Triplet Excited-State Geometries and Phosphorescence Energies of Heterocyclic Compounds: Comparison Between TD-PBE0 and SAC-CI. , 2014, Journal of chemical theory and computation.

[26]  Johannes Neugebauer,et al.  Direct determination of exciton couplings from subsystem time-dependent density-functional theory within the Tamm-Dancoff approximation. , 2013, The Journal of chemical physics.

[27]  Donald G Truhlar,et al.  Performance of recent and high-performance approximate density functionals for time-dependent density functional theory calculations of valence and Rydberg electronic transition energies. , 2012, The Journal of chemical physics.

[28]  D. Truhlar,et al.  Performance of the M11 and M11-L density functionals for calculations of electronic excitation energies by adiabatic time-dependent density functional theory. , 2012, Physical chemistry chemical physics : PCCP.

[29]  Martin Schütz,et al.  Molpro: a general‐purpose quantum chemistry program package , 2012 .

[30]  Yan Zhao,et al.  On the Performances of the M06 Family of Density Functionals for Electronic Excitation Energies. , 2010, Journal of chemical theory and computation.

[31]  Carlo Adamo,et al.  Extensive TD-DFT Benchmark: Singlet-Excited States of Organic Molecules. , 2009, Journal of chemical theory and computation.

[32]  Walter Thiel,et al.  Benchmarks for Electronically Excited States: A Comparison of Noniterative and Iterative Triples Corrections in Linear Response Coupled Cluster Methods: CCSDR(3) versus CC3. , 2009, Journal of chemical theory and computation.

[33]  W. Domcke,et al.  Efficient excited-state deactivation of the Gly-Phe-Ala tripeptide via an electron-driven proton-transfer process. , 2009, Journal of the American Chemical Society.

[34]  M. Head‐Gordon,et al.  Long-range corrected hybrid density functionals with damped atom-atom dispersion corrections. , 2008, Physical chemistry chemical physics : PCCP.

[35]  F. Bayrakçeken.  Triplet-triplet optical energy transfer from benzophenone to naphthalene in the vapor phase. , 2008, Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy.

[36]  Walter Thiel,et al.  Benchmarks for electronically excited states: CASPT2, CC2, CCSD, and CC3. , 2008, The Journal of chemical physics.

[37]  Trygve Helgaker,et al.  Excitation energies in density functional theory: an evaluation and a diagnostic test. , 2008, The Journal of chemical physics.

[38]  D. Truhlar,et al.  The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals , 2008 .

[39]  A. Voityuk,et al.  MS-CASPT2 calculation of excess electron transfer in stacked DNA nucleobases. , 2007, The journal of physical chemistry. A.

[40]  X. Assfeld,et al.  Comparison of theoretical approaches for predicting the UV/Vis spectra of anthraquinones , 2007 .

[41]  Donald G Truhlar,et al.  Density functional for spectroscopy: no long-range self-interaction error, good performance for Rydberg and charge-transfer states, and better performance on average than B3LYP for ground states. , 2006, The journal of physical chemistry. A.

[42]  Donald G Truhlar,et al.  Comparative DFT study of van der Waals complexes: rare-gas dimers, alkaline-earth dimers, zinc dimer, and zinc-rare-gas dimers. , 2006, The journal of physical chemistry. A.

[43]  Andreas Dreuw,et al.  Single-reference ab initio methods for the calculation of excited states of large molecules. , 2005, Chemical reviews.

[44]  G. Scuseria,et al.  Prescription for the design and selection of density functional approximations: more constraint satisfaction with fewer fits. , 2005, The Journal of chemical physics.

[45]  S. Farid,et al.  Chain amplification in photoreactions of N-alkoxypyridinium salts with alcohols: mechanism and kinetics. , 2005, The Journal of organic chemistry.

[46]  M. Robb,et al.  Key Role of a Threefold State Crossing in the Ultrafast Decay of Electronically Excited Cytosine , 2004 .

[47]  N. Handy,et al.  A new hybrid exchange–correlation functional using the Coulomb-attenuating method (CAM-B3LYP) , 2004 .

[48]  J. Fabian,et al.  Calculation of excitation energies of organic chromophores: a critical evaluation , 2002 .

[49]  Stefan Grimme,et al.  Comparison of multireference Møller-Plesset theory and time-dependent methods for the calculation of vertical excitation energies of molecules , 2002 .

[50]  D. Cremer,et al.  Can Unrestricted Density-Functional Theory Describe Open Shell Singlet Biradicals? , 2002 .

[51]  M. Reiher,et al.  Reparameterization of hybrid functionals based on energy differences of states of different multiplicity , 2001 .

[52]  Shinichiro Nakamura,et al.  Calculation of the absorption wavelength of dyes using time-dependent density-functional theory (TD-DFT) , 2000 .

[53]  D. Cremer,et al.  An Accurate Description of the Bergman Reaction Using Restricted and Unrestricted DFT: Stability Test, Spin Density, and On-Top Pair Density† , 2000 .

[54]  M. Head‐Gordon,et al.  Time-dependent density functional study on the electronic excitation energies of polycyclic aromatic hydrocarbon radical cations of naphthalene, anthracene, pyrene, and perylene , 1999 .

[55]  V. Barone,et al.  Toward reliable density functional methods without adjustable parameters: The PBE0 model , 1999 .

[56]  N. Handy,et al.  Excitation energies of benzene from Kohn–Sham theory , 1999 .

[57]  Nicholas C. Handy,et al.  Excitation energies of benzene from Kohn-Sham theory , 1999, J. Comput. Chem..

[58]  G. Scuseria,et al.  An efficient implementation of time-dependent density-functional theory for the calculation of excitation energies of large molecules , 1998 .

[59]  B. Roos,et al.  A Theoretical Study of the Indigoid Dyes and Their Chromophore , 1997 .

[60]  Poul Jørgensen,et al.  Perturbative triple excitation corrections to coupled cluster singles and doubles excitation energies , 1996 .

[61]  Gross,et al.  Excitation energies from time-dependent density-functional theory. , 1996, Physical review letters.

[62]  K Schulten,et al.  VMD: visual molecular dynamics. , 1996, Journal of molecular graphics.

[63]  Ove Christiansen,et al.  Response functions in the CC3 iterative triple excitation model , 1995 .

[64]  Poul Jørgensen,et al.  The second-order approximate coupled cluster singles and doubles model CC2 , 1995 .

[65]  Björn O. Roos,et al.  Second-order perturbation theory with a complete active space self-consistent field reference function , 1992 .

[66]  A. N. Díaz,et al.  Absorption and emission spectroscopy and photochemistry of 1,10-anthraquinone derivatives: a review , 1990 .

[67]  Kerstin Andersson,et al.  Second-order perturbation theory with a CASSCF reference function , 1990 .

[68]  E. Gross,et al.  Density-Functional Theory for Time-Dependent Systems , 1984 .

[69]  N. Nakatsuji,et al.  Cluster expansion of the wavefunction. Excited states , 1978 .

[70]  K. Stika,et al.  Luminescence determination of pharmaceuticals of the tetrahydrocarbazole, carbazole, and 1,4-benzodiazepine class. , 1976, Analytical chemistry.

[71]  H. H. Richtol,et al.  Triplet state acidity constants for hydroxy and amino substituted anthraquinones and related compounds. Comparison of phosphorescence and transient triplet absorption measurements , 1974 .

[72]  A. Fetter,et al.  Quantum Theory of Many-Particle Systems , 1971 .

[73]  W. Kohn,et al.  Self-Consistent Equations Including Exchange and Correlation Effects , 1965 .

[74]  Mostafa A. El-Sayed,et al.  Spin—Orbit Coupling and the Radiationless Processes in Nitrogen Heterocyclics , 1963 .