Electronic structure of the azide ion using the SCF Xα SW method

The electronic structure of the azide ion is investigated using the SCF Xα scattered wave method. Calculated ionization energies are compared with values determined by electron spectroscopy. Transition state calculations for π_g → π*_u, σ_u → π*_u and σ_g → π*_u single electron transitions yield excitation energies near 5.7, 11.0, and 12.0 eV respectively.     

The electronic spectrum of benzene

Assignment of the benzene spectrum is discussed using a new approach to the semi-empirical π-electron theory. The ordering ¹B_1u <¹E_1u <¹E_2g is shown to be theoretically preferred.     

Enhanced Optical Properties of Azaborole Helicenes by Lateral and Helical Extension

The synthesis and characterization of laterally extended azabora[5]-, -[6]- and -[7]helicenes, assembled from N-heteroaromatic and dibenzo[g,p]chrysene building blocks is described. Formally, the π-conjugated systems of the pristine azaborole helicenes were enlarged with a phenanthrene unit leading to compounds with large Stokes shifts, significantly enhanced luminescence quantum yields (Φ) and dissymmetry factors (g_lum). The beneficial effect on optical properties was also observed for helical elongation. The combined contributions of lateral and helical extensions resulted in a compound showing green emission with Φ of 0.31 and |g_lum| of 2.2×10⁻³, highest within the series of π-extended azaborahelicenes and superior to emission intensity and chiroptical response of its non-extended congener. This study shows that helical and lateral extensions of π-conjugated systems are viable strategies to improve features of azaborole helicenes. In addition, single crystal X-ray analysis of configurationally stable [6]- and -[7]helicenes was used to provide insight into their packing arrangements.     

π* ← n electronic absorption spectrum of 2,6-dichloropyrazine

The π* ← n electronic absorption system of 2,6-dichloropyrazine, corresponding to the ¹B_3u ← ¹A_1g transition of pyrazine, has been recorded in the vapour phase and in solution in cyclohexane. A vibrational analysis of this system has been proposed and it is shown that vibronic interaction between two excited states of 2,6-dichloropyrazine exists. Another system is observed in the solution spectrum of this molecule in cyclohexane and it is shown to be a π* ← π transition analogous to the ¹B_2u ← ¹A_1g transition in pyrazine.     

Tetrakis (methylidene)cyclobutane (‘[4]Radialene’): Electronic states of the molecular ion

The photoelectron spectrum of tetrakis (methylidene)cyclobutane ( 1 , ‘[4]radialene’) is reported. The electronic states of 1 ⁺ are assigned on the basis of model calculations and with reference to related systems. Jahn-Teller activity in the degenerate states is discussed. A failure of the simple LCBO-model for the π(e_g)-orbital of 1 is noted and traced to the fact that this orbital, though having a symmetry-equivalent π*-counterpart, does not interact with it. This feature is confined to [4n]radialenes; their total π-energies are therefore higher than those of the other members. It is shown that radialenes, in principle, do not constitute a class analogous to that of the linear polyenes as inferred earlier.     

Angular overlap parameters for ruthenium(II) complexes

Approximate Angular Overlap Model e_π parameters have been obtained for a number of ligands L by comparison of the t_2g(Ru) → π^*(bpy) transition energies in [Ru(bpy)₂L₂] complexes. The filled t_2g subshell of Ru(II) limits the effects of otherwise strongly π-donating ligands.     

AB initio and configuration interaction calculations for some σ → π* superexcited states of the trans-1,3-butadiene molecule

Some σ → π¹ superexcited states of the trans-1,3-butadiene molcule have been calculated in order to establish them as possible candidates for the 9.52 eV and 11.04 eV transitions observed in the electron impact spectra of this molecule. Four states have been solved self-consistently ( 7a_g→ 2a_u2a_gand 2b_g and 6b_u→ 2a_u, 2bg) and on the basis of extensive CI calculations of transition energies and oscillator strengths, we assign the 11.04 eV transition to the ¹B_g (6b_u→ 2a_u) state. The transition observed at 9.52 eV is more likely to be either a π (la_u) → π1 transition or the first member of a Rydberg series converging to the second ionization potential.     

Photoelectron spectrum of hypofluorous acid,HOF

The photoelectron spectrum of HOF has been obtained with He I resonance radiation. Three bands were observed, which can be interpreted by analogy to the diatomic halogens, and to the recently reported CIF. The first two bands can be identified with the out-of-plane and in-plane components of the π_g-like outermost orbital of the diatomic halogens, split by the C_s symmetry of HOF. The first ionization potential is found to be 12.69 ± 0.03 eV, in close agreement with the photoionization value 12.71 ± 0.01 eV.     

Constructing a novel nonlinear optical materials: substituents and heteroatoms in π-π systems effect on the first hyperpolarizability

By doping π-π systems with Li atom, a series of Li@sandwich configuration and Li@T-shaped configuration compounds have been theoretically designed and investigated using density functional theory. It is revealed that energy gaps (E _gap) between highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of all compounds are in a range of 0.4–0.9 ev. When Li atom is introduced into different sandwich configuration π-π systems (C₆₀-toluene, C₆₀-fluorobenzene, C₆₀-phenol, C₆₀-benzonitrile), Li@C₆₀-benzonitrile exhibits considerable first hyperpolarizability as large as 19,759 au, which is larger by about 18,372–18,664 au than those of other compounds. When Li atom is introduced into different T-shaped configuration π-π systems (C₆₀-pyridine, C₆₀-pyrazine, C₆₀-1, 3, 5-triazine, C₆₀-pyridazine), Li@C₆₀-pyridazine is found to present largest first hyperpolarizability up to 67,945 au in all compounds. All compounds are transparency in the deep ultraviolet spectrum range. We hope that this study could provide a new idea for designing nonlinear optical materials using π-π systems as building blocks.     

Assignment of the four lowest ionized states of p-benzoquinone and the question of “lone pair splitting” in this system

The lowest ionized states of p-benzoquinone are assigned to be n_/²B_3g, n₄/²B_2u, π₁/²B_3u, and π₂/²B_1g in order of increasing energy. This sequence of states confirms Turner's original assignment and invalidates subsequent proposals. The origin of the difficulties with these assignments are traced back to the non-validity of Koopmans' theorem for the “oxygen lone pair” ionizations (i.e., ionization to the n_/²B_3g and n₊/²B_2u states).     

Circulardichroism—LXXV: Cottonogenic derivatives of chiral bidentate ligands with the complex [Mo2 (O2CCH3)4]

[Mo₂(O₂CCH₃)₄] forms optically active complexes in DMSO after addition ofchiral ligands. Bidentate ligands (carboxylic acids, diols, and amino alcohols) but also a primary amine (α-phenylethylamine) were shown to form these complexes. For molar ratios of less than appr. 1.5:1 (ligand to complex) up to 5 Cotton effects (A to E from 600 to 270 nm) can be observed. The signs of those between 300 and 400 nm can be used for empirical determination of absolute configuration of complexing ligands. Bands A-D are assigned to the following transitions: A: mainly π_Mo-Mo→ δ^* (A_1g→ E_g); B: δ →ρ^*_Mo-O (A_1g → A_2g C: mainly δ → π^*_Mo-Mo (A_1g → E_g ) D: δ → δ^* (A_1g → A_2u ). Sector rules for the pair of CD-bands A/C (hexadecant rule) and for CD-band B (hexadecant rule with two additional nodal planes through the MoO_4- planes) are derived from qualitative MO theory.     

Photoelectron-spectroscopic Evidence Concerning “Homo-aromaticity”

The first of the two π-bands in the photoelectron spectrum of cis-cis-cis-1, 4, 7-cyclononatriene (I, symmetry C_3v) shows a Jahn-Teller split. This is consistent with the prediction of molecular orbital theory that the top occupied orbitals of I are e (π) and a ₁(π) respectively. From the difference ?( e (π)) - ?( a ₁(π)) = 0.90 to 0.97 eV a value of β_1,3 = ?0.68 eV = 0.27 β (β = -2.5 eV) is obtained for the homoconjugative interaction of two π-orbitals in I. This value represents almost exclusively through-space interaction between the π-orbitals. Through-bond interaction (hyperconjugation) is a minor effect in I. A comparison of the photoelectron data of bicyclo [4.2.1] nonatriene with those of norbornene and cycloheptadiene shows that homoconjugation (homo-aromaticity) can only be detected by photoelectron spectroscopy if the interacting π-bonds (basis orbitals) are symmetry equivalent or have accidentally (almost) degenerate energies.     

The electronic structure and optical activity of conjugated dienes: 1,3-Butadiene and α- and β-phellandrene

The optical activity of conjugated dienes is investigated by means of ab initio SCF–CI calculations. The computed electronic spectrum of trans-1,3-butadiene is shown to be in good agreement with the results of more rigorous calculations of the valence transitions and in satisfactory agreement with experiment. The optical rotatory strengths of the lower electronic transitions of twisted 1,3-butadiene as a function of dihedral angle are presented and simulated CD spectra are produced. The N → V₁ (π₂ → π₃*) transition is predicted to have a positive rotational strength for all dihedral angles that correspond to a right-handed twist of the chromophore, in accord with the empirically deduced “diene rule” although for a twist angle of 60°, the rotatory strength is calculated to be almost zero. The role of the orientation of allylic bonds is investigated in the model system 1-butene in which the rotational strength of the π → π* transition as a function of rotation about the 2,3 bond is determined. The effect of allylic bond disposition in dienes on the optical activity of the long-wavelength π₂ → π₃* transition is simulated by use of the exciton coupling model of Harada and Nakanishi in which two 1-butene molecules with suitable geometries are coupled via interactions of the electric dipole transition moments of their π → π* transitions. The model systems 1,3-butadiene and 1-butene are used to rationalize the apparently anomalous optical activity of (?)-α-phellandrene and (?)-β-phellandrene, both of which should have a diene chromophore with a right-handed twist in their most stable conformers and so should be dextrorotatory. The experimental CD spectrum of α-phellandrene is determined at several temperatures down to ?180°C. The observed variation of the apparent rotational strength of the N → V₁ transition is in good agreement with that predicted by use of the exciton coupling model.     

Schwingungs-Raman-Spektren von Hexahalogenokomplexen von OsIV (X = Cl,I) und IrIV (X = Cl,Br) bei 80 K

Vibrational Raman Spectra of Hexahalo Complexes of Os^IV (X = Cl, I) and Ir^IV (X = Cl, Br) at 80 K The Resonance-Raman (RR) spectra of the tetrabutyl- resp. tetraethylammonium salts of [OsCl₆]^2?, [OsI₆]^2?, [IrCl₆]^2?, and [IrBr₆]^2? have been investigated with the excitation-lines of an Ar⁺ and Kr⁺ laser. Devices with a movable sample holder for low-temperature experiments (80 K) are described. The anormal intensities of some of the Ra-active fundamentals are attributed to the RR effect. As a rule the deformation vibration υ₅(T_2g) is RR enhanced if excited within a π—π*(dt_2g)-CT-transition and the stretching vibration υ₂(E_g) is RR-enhanced within a π—σ*(de_g)-CT-transition. The dispersion of the degree of depolarisation of the three Ra-active fundamentals of [IrBr₆]^2? demonstrates, that this rule cannot only be applicated to the symmetrical but also to the antisymmetrical part of the scattering tensor.     

Nuclear quadrupole resonance in a single crystal of dimethyltin dichloride

The Zeeman NQR spectrum of a single crystal of dimethyltin dichloride has been reinvestigated in view of an improved determination of the crystal structure. The study shows the existence of two zero-splitting loci for the chlorine atoms. The quadrupole coupling constant was found to be ?30.92 MHz with an asymmetry parameter of η = 0.32. The principal EFG Z-axes are coincidental with the SnCl bonds, the Y-axes parallel to the crystallographic b-axis and the X-axes lie in the cb-plane. Using the Townes Dailey theory the fraction of π-bonding was calculated to be 0.24 with π_y-π_x = ?0.06. The imbalance in the π-bonding is rationalized on the basis of d-p overlap between the chlorine p_y-orbitals and the tin d-orbitals.     

Excited-state absorption of mono-, di- and tri-nuclear cyclometalated platinum 4,6-diphenyl-2,2′-bipyridyl complexes

The ground-state absorption cross-sections (σ_g), triplet excited-state absorption cross-section (σ_T) at 532 nm, singlet excited-state absorption cross-sections (σ_s) at various visible wavelengths, singlet and triplet excited-state lifetimes, and triplet quantum yields of three cyclometalated platinum(II) 4,6-diphenyl-2,2′-bipyridyl complexes, are reported. The presence of metal-metal and π-π interactions in the dinuclear and trinuclear complexes results in a significant increase in their respective σ_g’s in the visible spectral region. As a result, the ratio of σ_s/σ_g and σ_T/σ_g at each wavelength is significantly greater for the mononuclear complex than for the dinuclear and the trinuclear complexes.     

Partial cross sections and density-of-states effects in the valence-band photoemission from solid nitrogen

Photoelectron energy distribution curves from solid nitrogen were measured for excitation energies to 40 cV using synchrotron radiation. Partial cross sections for emission from 3σ_g, 1π_u and 2σ_u derived valence bands show pronounced mauna 3, 4, 2.9 and 3.0 eV above the vacuum levels, interpreted as due to high density of conduction-band final states. These states are related to π*_g negative-ion shape resonances.     

The EPR spectrum of O on magnesium oxide

The EPR spectrum of O⁻ on MgO has been observed following the reaction of N₂O with electrons trapped at the surface. The spectrum of the ion in axial symmetry is characterized by g_⊥ = 2.041 and g_∥ = 2.0016. Upon exposure to H₂, CO, CO₂ or additional N₂O the spectrum is replaced by another having g₁ = 2.0172, g₂ = 2.0100 and g₃ = 2.0014. This spectrum is tentatively assigned to the O₃⁻ ion.     

ESR study of the generation and decay of peroxy radicals in mechanically destructed polyamide 6

Polyamide 6 has been mechanically destructed in vacuo. At -70°, the ESR spectrum corresponds to the sum of the component spectra of three radicals NH?HCH₂, ·CH₂NHCO, and ·CH₂CONH. After introducing air into the ampoule, the spectrum changes even at -70°; the changes have been studied up to 0°. The spectrum of the peroxy radical ROO· (with line width 1.57 mT, g₁ = 2.0089 and g_| = 2.0301) predominates.