Search results for "SINGLET"
showing 10 items of 352 documents
Countably compact weakly Whyburn spaces
2015
The weak Whyburn property is a generalization of the classical sequential property that was studied by many authors. A space X is weakly Whyburn if for every non-closed set \({A \subset X}\) there is a subset \({B \subset A}\) such that \({\overline{B} \setminus A}\) is a singleton. We prove that every countably compact Urysohn space of cardinality smaller than the continuum is weakly Whyburn and show that, consistently, the Urysohn assumption is essential. We also give conditions for a (countably compact) weakly Whyburn space to be pseudoradial and construct a countably compact weakly Whyburn non-pseudoradial regular space, which solves a question asked by Angelo Bella in private communica…
Substituent-induced coupling of the two lowest excited singlet states of 2-methoxy-derivatives of 4-(N,N-dimethylamino)- and 4-(N-methylamino)benzoni…
2002
The title compounds both exhibit strong features of interaction of their two lowest excited states, but only one of them, the dimethylamino derivative, exhibits dual fluorescence. This is a direct indication that state interaction and dual fluorescence are not directly related.
Flexible diphenylsulfone versus rigid dibenzothiophene-dioxide as acceptor moieties in donor-acceptor-donor TADF emitters for highly efficient OLEDs
2020
DG acknowledges funding from the ERDF PostDoc project No. 1.1.1.2/VIAA/1/16/177 . This research is/was funded by the European Regional Development Fund according to the supported activity ‘ Research Projects Implemented by World-class Researcher Groups ’ under Measure No. 01.2.2-LMT-K-718 . Ministry of Science and Technology (MOST), Taiwan , Grant No. MOST 106-2923-E-155-002-MY3 . This work was also supported by the Ministry of Education and Science of Ukraine (projects no. 0117U003908 and 0118U003862 ), and by the Olle Engkvist Byggmästare foundation (contract No. 189-0223 ). The quantum-chemical calculations were performed with computational resources provided by the High Performance Comp…
Electron Transfer from the Singlet and Triplet Excited States of Ru(dcbpy)2(NCS)2into Nanocrystalline TiO2Thin Films
2002
Time-resolved absorption spectroscopy was used to study the femtosecond and picosecond time scale electron injection from the excited singlet and triplet states of Ru(dcbpY)(2)(NCS)(2) (RuN3) into titanium dioxide (TiO2) nanocrystalline particle film in acetonitrile. The fastest resolved time constant of similar to30 fs was shown to reflect a sum of two parallel ultrafast processes, nonergodic electron transfer (ET) from the initially excited singlet state of RuN3 to the conduction band of TiO2 and intersystem crossing (ISC). The branching ratio of 1.5 between the two competing processes gives rate constants of 1/50 fs(-1) for ET and 1/75 fs(-1) for ISC. Following the ultrafast processes, a…
Ab initio calculations of zero-field splitting parameters in linear polyacenes
2003
Abstract The results of ab initio calculations of zero-field splitting (ZFS) parameters are presented for the linear polyacenes from benzene to pentacene. We show how the electron spin–spin (SS) parameters can be efficiently obtained from restricted high-spin open-shell wave functions (ROHF), and present calculations of these, comparing with the results of a recent multi-configurational self-consistent field approach. The SS parameters are obtained from electron SS coupling strengths evaluated as expectation values over the wave functions and from state-to-state spin–orbit (SO) interactions. The results for the two lowest triplet states of naphthalene demonstrate that excellent values can b…
Linear and nonlinear optical properties of a series of Ni-dithiolene derivatives
2009
Some linear and nonlinear optical (NLO) properties of Ni(SCH)4 and several of its derivatives have been computed by employing a series of basis sets and a hierarchy of methods (e.g., HF, DFT, coupled cluster, and multiconfigurational techniques). The electronic structure of Ni(SCH)4 has been also analyzed by using CASSCF/CASPT2, ab initio valence bond, and DFT methods. In particular we discuss how the diradicaloid character (DC) of Ni(SCH)4 significantly affects its NLO properties. The quasidegeneracy of the two lowest-energy singlet states 1 mathg and 1 math1u, the clear DC nature of the former, and the very large number of low-lying states enhance the NLO properties values. These particul…
Spin State and Ligand Dissociation in [CpCoL2] Complexes (L = PH3, H2C=CH2): A Computational Study
1999
International audience; The relative energies of [CpCoL] compounds (L = PH3, H2C=CH2) were calculated at the DFT/B3LYP level of theory. The triplet spin state was found to be favored over the singlet by between 33.0 and 21.0 kcal mol−1 for both fixed and optimized geometries. The basis set size was found to be important for the energy calculations, particularly when the energetics of ligand dissociation was examined. The role of the triplet spin state in facilitating the ligand dissociation process is discussed.
Towards an accurate molecular orbital theory for excited states : Ethene, butadiene, and hexatriene
1993
A newly proposed quantum chemical approach for ab initio calculations of electronic spectra of molecular systems is applied to the molecules ethene, trans‐1,3‐butadiene, and trans‐trans‐1,3,5‐hexatriene. The method has the aim of being accurate to better than 0.5 eV for excitation energies and is expected to provide structural and physical data for the excited states with good reliability. The approach is based on the complete active space (CAS) SCF method, which gives a proper description of the major features in the electronic structure of the excited state, independent of its complexity, accounts for all near degeneracy effects, and includes full orbital relaxation. Remaining dynamic ele…
Counterintuitive Mechanisms of the Addition of Hydrogen and Simple Olefins to Heavy Group 13 Alkene Analogues
2013
The mechanism of the reaction of olefins and hydrogen with dimetallenes ArMMAr (Ar = aromatic group; M = Al or Ga) was studied by density functional theory calculations and experimental methods. The digallenes, for which the most experimental data are available, are extensively dissociated to gallanediyl monomers, :GaAr, in hydrocarbon solution, but the calculations and experimental data showed also that they react with simple olefins, such as ethylene, as intact ArGaGaAr dimers via stepwise [2 + 2 + 2] cycloadditions due to their considerably lower activation barriers vis-à-vis the gallanediyl monomers, :GaAr. This pathway was preferred over the [2 + 2] cycloaddition of olefin to monomeric…
A worrisome failure of the CC2 coupled-cluster method when applied to ozone
2010
Abstract The approximate coupled-cluster singles and doubles model CC2 is widely used for calculations of excited states in large molecules. We demonstrate a surprising failure of the CC2 geometry optimization of ozone, whereby the CC2 method predicts a barrierless, exothermic, and symmetric dissociation to three oxygen atoms. This is particularly astonishing since both second-order Moller–Plesset perturbation theory and coupled-cluster singles and doubles give reasonable equilibrium structures. We find that [ [ H , T 1 ] , T 1 ] leads to an unbalanced treatment of T 1 and T 2 in the CC2 equations. Results presented here suggest that considerable caution should be exercised when applying th…