Energetics,electronic structures and geometries of naphthalene,quinoline and isoquinoline analogues of 1,2-didehydrobenzene

B3LYP/cc-pVTZ electronic structure calculations employed in conjunction with additive corrections derived from experimental data for 1,2-didehydrobenzene predict the standard enthalpies of formation of 1,2- and 2,3-didehydronaphthalenes to be equal to 121.0 and 123.7 kcal mol^?1, respectively. The corresponding singlet-triplet splittings amount to 40.1 and 35.4 kcal mol^?1. The positional dependence of both of these quantities is preserved in those didehydroquinolines and didehydroisoquinolines in which the didehydrogenation sites are separated by at least one carbon from the heteroatoms. The effect of the adjacent heteroatoms on the singlet-triplet splittings is significantly more pronounced than that on the standard enthalpies of formation. Test G3 calculations on 2,3-didehydronaphthalene confirm the reliability of the additive correction scheme in the prediction of properties of annelated analogues of 1,2-didehvdrobenzene. Such a scheme opens an avenue to facile electronic structure calculations on didehydrogenation reactions of polycondensed heterocyclic compounds with six-membered rings.     

Mechanistic study of the unimolecular decomposition of 1,2‐dioxetanedione

The unimolecular decomposition of 1,2‐dioxetanedione, the high‐energy intermediate of the chemiluminescence peroxyoxalate reaction, was studied by theoretical means for the first time. Our calculations have provided results in line with the experimental data regarding this compound. 1,2‐Dioxetanedione decomposes due to a step‐wise biradical mechanism. In the biradical region of the decomposition path, there is a path for singlet chemiexcitation. Interactions between the singlet ground and excited states with triplet states can explain the weak unimolecular chemiluminescence of 1,2‐dioxetanedione. Copyright © 2013 John Wiley & Sons, Ltd.     

Electronic and magnetic properties of graphene nanoribbons

Molecular orbital calculations of the electronic properties of graphene nanoribbons as a function of length in the nanometre range show a pronounced decrease in the band gap and ionization potential with increasing length. It is shown that length can be used to design the materials to be insulating, semiconducting or metallic. A low ionization potential (work function), less than single walled carbon nanotubes, is obtained at the longest length of the calculation (2.3?nm). This latter result suggests the possibility of using graphene nanoribbons as electric field induced electron emitters. Calculations on boron and nitrogen doped carbon nanoribbons indicate that the triplet state is more stable than the singlet state.     

Low-lying excited states and photodissociation studies of cis-BrONO

A computational study of the low-lying singlet and triplet states of bromine nitrite, cis-BrONO, is presented. Calculations of excitation energies and oscillator strengths are reported using multi-reference configuration interaction, MRD-CI, methods in conjunction with the cc-pVDZ?+?sp and cc-pVTZ?+?sp basis sets. In agreement with recent experimental work the calculations find two important transitions, namely to the states 2¹ A′ at 3.99?eV and 4¹ A′ at 5.27?eV. The corresponding measurements obtained 3.87 and 5.44?eV, respectively. Both states show multi-reference character, representing a linear combination of 3a″?→?4a″ and 9a′?→?10a′ transitions. The potential energy curves for the Br+ONO dissociation are repulsive for both states indicating possible photodissociation. BrO+NO products are not favoured because the corresponding potential energy curves show barriers on the order of 0.5?eV.     

Experimental and theoretical study of dicyanocarbene C(CN)2

Dicyanocarbene C(CN)₂ and its radical cation (m/z 64) were generated by dissociative ionization of tetracyanoethene, dicyanofuroxan and dicyanofurazan and characterized by collisional activation (CA) and neutralization-reionization (NR) mass spectrometries and tandem MS³ experiments performed in a ‘hybrid’ tandem mass spectrometer having a sector-quadrupole-sector configuration. In both neutral and ionized forms, dicyanocarbene is found to be a stable and detectable species. Existence of the peaks at m/z 52, 24 and 12 in the CA/NR spectra suggests however some possible post-collisional rearrangements. The carbene was further studied by ab initio calculations using B3LYP/6-311+G(3df) for geometries and CASPT2(14,12) and MR-SDCI with the cc-pVTZ and aug-cc-pVTZ basis sets for relative energies. The dicyano form NC-C-CN is consistently more stable than its isocyano isomers CN-C-CN and CN-C-NC, irrespective of the electronic state. Each neutral carbene exhibits a triplet ground state lying up to 2.6 eV below the singlets. All the triplet, singlet and ionized states of dicyanocarbene have a linear shape. The other states have either linear or bent shape but small barriers to linearity. Adiabatic ionization energies (IE_a) were estimated as follows: NC-C-CN: 11.3 eV with linear ²Π_u cation; NC-C-NC: 10.4 eV with linear ²Π cation, and CN-C-NC: 9.9 eV with bent ²A₁ cation.     

HFSiS构型及其稳定性的理论研究

利用密度泛函理论对三线态HFSiS分子结构及其稳定性进行了详细的理论研究.在B3LYP/6-311G**水平上计算出了各驻点的优化构型、振动频率,并对各个振动模式加以归属,在同样的理论水平上进行了IRC计算;CCSD(T)结合6-311G**基组对于驻点进行单点能及相对能量的计算;根据振动模式分析来阐明三线态势能面上各驻点之间的变化,并与单线态势能面进行比较.计算结果表明,三线态HFSiS分子存在6种异构体,3HFSiS结构在动力学和热力学上都是最稳定的,实验上应该可以观测到;在两组键旋转异构体当中,结构-2具有一定的动力学稳定性,而结构-1动力学稳定性较差;3SiSHF在动力学上和热力学上都是最不稳定的结构.     

Level structures in the odd-odd nucleus180Re

Experimental data on energy levels of the odd-odd deformed nucleus¹⁸⁰Re obtained from radioactive-decay and heavy-ion reaction studies are analysed to deduce spin-parity and configuration assignments for the six observed rotational bands based on the selection rules for fast beta transitions, criteria for the relative-energy ordering of the triplet and singlet bandheads, two-particle-plus-rotor model calculations including Coriolis mixing, rotational energy systematics involving staggering features, and considerations of gyromagnetic ratios, signature splittings and rotational band alignments.     

Increasing the B/N ratio in boron nitride nanoribbons,a possible approach to dilute magnetic semiconductors

Density functional theory (DFT) employing the local spin density approximation and including correlation functionals is used to show that increasing the boron content relative to the nitrogen content in boron nitride nanoribbons can significantly reduce the band gap making the ribbons semiconducting. Armchair ribbons, but not zigzag ribbons, having excess borons are predicted to have a more stable optimized triplet structure than the optimized singlet structure. The triplet structure is predicted to have a higher density of states at the top of the valence band near Fermi level for the spin down state indicating it could be a ferromagnetic semiconductor. The results suggest a possible new approach to developing ferromagnetic semiconductors.     

The probabilities of triplet-singlet transitions in aromatic hydrocarbons and ketones

Calculations have been performed on the probabilities of triplet-singlet transitions in benzene and acetone in connection with the decay times of the phosphorescence. The transition probability was determined from the extent to which excited singlet states are mixed with the triplet state. The assumption that in benzene the phosphorescent state has ³ B_2u properties—so that the ¹ B_1u singlet state is mixed with it-—yields the best agreement with the experimental data. In the case of acetone the phosphorescence was considered as a triplet-singlet transition in which only the electrons of the CO group are involved. In both cases the agreement with experiment is as satisfactory as in other calculations on transition probabilities, the figures for the decay times being 190 and 7 seconds for benzene and 7·8 and 0·6 milliseconds for acetone. The ratio of the calculated decay times is in good agreement with the experimental result (2·4×10⁴ and 1·2×1O⁴).     

Highly accurate coupled-cluster singlet and triplet pair energies from explicitly correlated calculations in comparison with extrapolation techniques

Coupled-cluster singles and doubles (CCSD) valence shell correlation energies of the systems CH₂ (<¹A₁ state), H₂O, HF, N₂, CO, Ne, and F₂ are computed by means of standard calculations with correlation-consistent basis sets of the type cc-pVxZ (x = D, T, Q, 5, 6) and by means of explicitly correlated coupled-cluster calculations (CCSD-R12/B) with large uncontracted basis sets of the type 19s14p8d6f4g3h for C, N, O, F, and Ne and 9s6p4d3f for H. These CCSD-R12/B calculations provide reference values for the basis set limit of CCSD theory. The computed correlation energies are decomposed into singlet and triplet pair energies. It is established that the singlet pair energies converge as X^?3 and the triplet pair energies as X^?5 with the cardinal number of the correlation-consistent basis sets, and an extrapolation technique is proposed that takes into account their different convergence behaviour. Applied to the cc-pV5Z and cc-pV6Z results, this new extrapolation yields pair energies with a mean absolute deviation of 0.02 mE_h from the CCSD-R12/B reference values. For the seven systems under study, the extrapolated total valence shell correlation energies agree to within 0.2 mE_h with the CCSD-R12/B benchmark data.     

An investigation of the structure of free-base porphycene by time-resolved electron nuclear double resonance and density functional theory on the photoexcited triplet state

The photoexcited triplet state of free-base porphycene has been investigated by time-resolved electron nuclear double resonance spectroscopy at 10 K. In order to determine whether porphycene is cis or trans configured, experimentally determined A_zz hyperfine coupling tensor components are compared with those predicted from density functional theory. The structures of cis and trans porphycene, in both the singlet ground state and lowest excited triplet state were calculated using the Becke3-Lee-Yang-Parr composite exchange correlation functional and the 6–31G* basis set. Hyperfine couplings for these structures were then calculated using the same functional but with the extended EPR-II basis set. From the results it can be concluded that porphycene has a trans configuration in both the ground singlet and lowest excited triplet state. Additionally, the significant differences in structure between the singlet and triplet states are reflected in the calculated hyperfine couplings, with those for the trans conformation in the triplet state in reasonable agreement with the experimental values.     

Phase diagram and critical fields of organic quasi-1d superconductors in an applied magnetic field

No consensus has been reached about the symmetry of the Bechgaard salts superconducting phase. An RG analysis is in favor of interactions dominant in the singlet channel, but very close and sub-dominant in the triplet channel. We study the properties, in a magnetic field along the b′ direction, of a d-wave singlet phase, as well as of an f-wave triplet phase. Recent data about NMR Knight shift, as well as upper critical fields have brought strong indications about the possible symmetries. We have analyzed theoretically the consequences of these experimental data: our results are in favor of a singlet phase in low field, but of a triplet phase in large fields.     

Reaching for [6]n SiC‐cyclacenes and [6]n SiC‐acenes: A DFT approach

Density functional theory (DFT) calculations introduced triplet ground states for [6]_n SiC‐cyclacenes and ‐acenes with alternate silabenzene rings including silicon atoms in 2 opposite edges (n = 6, 8, 10, 12). The singlet‐triplet energy gap (ΔE_(S‐T)), binding energy per atom (BE/n), and NBO calculation with very small band gap (ΔE_LUMO‐HOMO) confirmed the triplet ground states. In contrast to polyacenes, the singlet [6]_n SiC‐cyclacenes displayed more stability improvement than triplets, through n increasing. This may open the way for synthesis of larger stable [6]_n SiC‐cyclacenes. The ΔE_(S‐T), BE/n, and the strain energy through homodesmic equations indicated more stability for larger [6]_n SiC‐cyclacenes, which was more noticeable in singlet states. Cyclacenes and acenes with high conductivity and full point charge were introduced as suitable candidates for hydrogen storage.     

O2 diffusion in SiO2: triplet versus singlet

We address the diffusion of the oxygen molecule in SiO2, using first-principles spin-polarized total-energy calculations. We find that the potential energy surfaces for the singlet and triplet states are very different in certain regions, and that the O2 molecule preserves its spin-triplet ground state not only at its most stable interstitial position inside the solid but also throughout its diffusion pathway. Therefore, the singlet state is not a good approximation to describe the behavior of O2 inside SiO2, and spin-polarization effects are fundamental to understand the properties of this system.     

The reactions of Cl+ (3P) and Cl+ (1D) with hydrogen sulphide. A G2 molecular orbital study

G2 ab initio molecular orbital calculations have been performed to study the potential energy surfaces (PESs) associated with the reactions of Cl⁺ in its ³P ground state and in its ¹D first excited state with hydrogen sulphide. [H₂, Cl, S]⁺ singlet and triplet state cations present very different bonding characteristics. The latter are systematically ion-dipole or hydrogen-bonded weakly bound species, while the former are covalent molecular ions. As a consequence, although the Cl⁺(³P) is 34.5 kcal mol^?1 more stable than Cl⁺(¹D), the global minimum of the singlet PES lies 37.3 kcal mol^?1 below the global minimum of the triplet PES. Both singlet and triplet potential energy surfaces show significant differences with respect to those associated with Cl⁺ + H₂O reactions as well as with SH₂ reactions with F⁺. In both cases, the major product should be SH⁺ ₂; SH⁺ and HCl⁺ being the minor products, in agreement with the experimental evidence. The estimated heat of formation for the most stable H₂SCl⁺ singlet state species is 198 ± 1 kcal mol^?1.     

Low Temperature Spectra of the ortho-POPOP Molecule: Additional Arguments of Its Flattening in the Excited State

Low temperature absorption and fluorescence spectra were measured for 1,2-bis-(5-phenyl-oxazolyl-2)-benzene (ortho-POPOP), a sterically hindered molecule, substantially non-planar in its ground state. Quantum-chemical calculations with the optimization of molecular geometry were made using the semiempirical AM1 method. The observed spectral changes, together with the obtained theoretical results, evidenced in favor of our previously made assumption about the considerable flattening of ortho-POPOP in the lowest singlet excited state. The data of spin-orbit coupling between singlet and triplet terms, which has been estimated in CNDO/S scheme, were used to calculate the efficiency of intersystem crossing in the studied molecule.     

Ylide stabilized carbenes: a computational study

High‐level Density Functional Theory calculations, coupled with appropriate isodesmic reaction, are employed to investigate the effects of α‐carbon, ammonium, phosphorus, and sulfur ylides, cyclization, and unsaturation on the stability, multiplicity, and reactivity of novel singlet (S) and triplet (T) carbenes. Among them the highly π‐donating α‐ammonium ylide is found to exert the highest stabilizing effect on the carbenic center. α‐Ammonium ylides resist dimerization and hydrogenation. They show wider singlet–triplet energy gap (ΔΕ_S–T), broader band gap (ΔΕ_HOMO–LUMO), and higher nucleophilicity compared to the reported stable N‐heterocyclic carbenes. Aromatic cyclic unsaturated ammonium, phosphorus, and sulfur ylide carbenes appear more stable than their saturated cyclic analogs which are in turn more viable than their acyclic counterparts. Copyright © 2014 John Wiley & Sons, Ltd.     

From acyclic dialkylcarbene to the unsaturated cyclic heteroatom substituted ones: a survey of stability

In regard to the worldwide interest in synthesis and application of stable carbenes, ab initio and DFT calculations (CCSD(T)/6‐311G*//QCISD/6‐31G* and B3LYP/AUG‐cc‐pVTZ//B3LYP/6‐31 + G* levels) are employed to reach at a series of symmetrically substituted diheteroatom carbenes. In this way the multiplicity, stability, and reactivity of diethylcarbene and its saturated and unsaturated cyclic congeners are compared and contrasted to the corresponding disilyl‐, diamino‐, diphosphino‐, dioxy‐, and dithiocarbenes. The investigations reveal the enlargement of the singlet–triplet energy gaps (ΔE_S‐T) in the order of (amino ≈ oxy) > thio > phosphino > alkyl > silyl. The observed trend is thoroughly analyzed applying appropriate isodesmic reactions which differentiate the substituent effects on each of the singlet and triplet states of all the carbenes. In contrast to previous reports, it is found that π‐donor/σ‐acceptor amino substituents stabilize not only the singlet but also the triplet states. The effects of cyclization and unsaturation are also probed in each series of the symmetrically substituted carbenes. The reactivity of the species is discussed in terms of nucleophilicity, electrophilicity, and proton affinity. Copyright © 2010 John Wiley & Sons, Ltd.     

Singlet and Triplet State Properties and Singlet Oxygen Yield of an Amino-Acyl-Quinoxalinone Yellow Dye

Amino-acyl-quinoxalinone yellow dyes are cyclised analogues of the yellow azomethine dyes developed for, and still used in, silver halide colour photography. Unlike image azomethine dyes, which are rapidly deactivated in their excited states by torsion about the azomethine bond, amino-acyl-quinoxalinone dyes have an interesting photophysics because torsion is not possible due to their cyclised structure. We report results from studies on singlet and triplet state properties, and singlet oxygen yields, of the yellow dye, 7-diethylamino-3-(2,2-dimethyl-propionyl)-5-methyl-1-phenyl-1H-quinoxalin-2-one, in polar and nonpolar solvents. The dye photophysics is characterised by a weak fluorescence, with a solvent dependent emission yield (Φ_F?≈?0.002–0.004), and short singlet state lifetime (τ_expt?≈?20–50 ps), both increasing by a factor of ≈2 in going from polar acetonitrile to non-polar dioxane as solvent. DFT ZINDO calculations show a transition involving significant electron transfer from the diethyl-amino group into the carbonyl region of the molecule. In solution, in the presence of oxygen, the triplet state decays almost exclusively by oxygen quenching, and singlet oxygen is produced in high yield (Φ_??≈?0.5–0.55). The triplet state absorbs across the 450–750 nm region with maxima around 480 and 650 nm, and moderate molar absorption coefficients (ca. 6000–8000 M^?1 cm^?1). In a glass at 77 K, triplet decay gives a red phosphorescence, with λ_max?≈?640–650 nm, and a ?≈?0.25 s lifetime. If singlet oxygen yields are a good indication of triplet yields, then internal conversion and intersystem crossing occur with roughly equal efficiency.