Simulated T ← S spectra of benzaldehydes as a function of the energy gap between the ππ and nπ levels

The T_1,2 ← S₀ spectra of benzaldehydes have been studied as a function of the energy separation between the vibrationless levels. It is shown that the spectra are very complicated in the region of ΔE[T₂⁰(nπ^*)-T₁⁰(ππ^*)] = 250–400 cm⁻¹, reflecting effective vibronic interferences between T₂⁰(0-0) and each of the ν₃₆-ν₃₃ out-of-plane vibrational levels of T₁⁰(ππ^*). The simulated spectra correspond to the observed spectra. In the case of T₁⁰ = ³nπ^* and T₂⁰ = ³ππ^* the spectral change is not so drastic as in the reverse case loc. cit. because the optical intensity generally concentrates in the longest wavelength band, i.e., the origin band of the T₁(nπ^*) ← S₀ transition. The simulation spectra are useful for interpretation of the absorption spectra in similar electronic structure systems of substituted benzaldehydes.     

Dehydrogenation of adenine induced by slow (<3 eV) electrons

Low energy (<3 eV) electrons impact to gas phase Adenine generates the dehydrogenated Adenine negative fragments, (A–H)⁻, and an H-atom neutral radical counterpart. Within the energy range of 0.7–2.8 eV, production of (A–H)⁻ arises from Dissociative Electron Attachment (DEA). In addition, a sharp peak is observed at near 0 eV. This peak is identified to arise from dissociative electron transfer reaction of SF₆⁻ (from the calibration gas) with Adenine.     

Substituent effects on some physicochemical properties of chalcones and their vinylogues

Carbonyl stretching frequencies (ν_CO), dipole moments (μ), longwave maxima (λ_max), half-wave potentials (°_1/2), and relative intensities (Z/Z₀) of benzoyl-ion in mass-spectra oftrans chalcones and their vinylogues of the general type PhCO(CH=CH)_nC₆H₄R-p (I) were measured. Contrary to the previously investigated polyenes of the type R(CH=CH)_nR′ (R′ = CHO or COOEt) variation of the substituent R in compounds I has little influence on properties of I in the ground state and a satisfactory linear relationship between (ν_CO) or μ and σ constants exists only in the case of I (n = 0, 1); the best correlation with σ⁺ indicates that the mesomeric mechanism plays a great part in the transmission of electronic effects. λ_max.,E_1/2, orZ/Z₀ of all series I (n = 0–3) correlate with σ_p or σ⁰ constants, and the separation of mesomeric and inductive effects by multiparametric correlation reveals that in this case inductive effect is of great importance in the transmission of electronic effects. These features were accounted for by the non-planar structure of molecules of I, which was confirmed by X-ray analysis of I (R = Br). The Pariser-Parr-Pople method has also been applied to the calculation of π-electronic density in molecules I and it was found that the introduction of various substituents in para position of I exercises a very little influence on the electronic distribution in compounds I.     

Crystal structure of Fe(η-C5H5BCMe3)2 a “problem structure”

The complex Fe(η⁶-C₅H₅CMe₃)₂ crystallizes in the centrosymmetric triclinic space group P (C_i¹; No. 2) with unit cell dimensions of a 8.770(1) Å, b 8.878(1) Å, c 11.991(1) Å, 107.56(1)°, β 90.85(1)°, γ 90.13(1)°, V 890.0(2) ų and Z = 2. A full sphere of data was collected on a four-circle diffractometer. The structure was solved and refined to R 7.93% for all 3155 independent reflections and R 4.98% for those 2002 data with | F₀ | > 6σ. | F₀ |. The molecules lie on crystallographic inversion centers at 0, 0, 0 and 1/2, 0, 1/2; the crystallographic asymmetric unit therefore consists of two independent half molecules. The molecule centered at 0, 0, 0 (molecule “A”) is ordered and well-defined; that centered on 1/2, 0, 1/2 (molecule “B”)is probably disordered, as indicated by larger “thermal parameters” and a greater range of apparent interatomic distances. Discussion em phasizes the geometry of molecule A, which has precise C_i symmetry with Fe(1A)-B(1A) 2.297(4) Å and Fe(1A)-C(ring) distances ranging from 2.057(6) Å to 2.138(4) Å.     

UV photodissociation of N-methylpyrrole: The role of πσ states in non-hydride heteroaromatic systems

The photophysics of jet-cooled N-methylpyrrole molecules following excitation to their first excited singlet state (the ¹A₂ state, arising from a 3s/σ^*←π electron promotion) has been investigated by resonance enhanced multiphoton ionisation spectroscopy, by measurements of wavelength resolved ‘action’ spectra for forming CH₃ photoproducts, and by velocity map imaging studies of these CH₃ products (in their v = 0 and v₂ = 1 vibrational levels). CH₃ products are observed at all excitation wavelengths within the NMP absorption band. Direct dissociation on the ¹A₂ potential energy surface (PES) yields ‘fast’ CH₃ fragments, with an average total kinetic energy release (TKER) of 6500 cm⁻¹, but this product channel is only observed in a narrow wavelength range near the absorption band origin. All of the measured CH₃ images also show a broad component, peaking at lower TKER (1700 cm⁻¹); this component extends beneath the ‘fast’ feature in images recorded at wavelengths near the origin, and accounts for all of the CH₃ products observed at shorter photolysis wavelengths. These products are attributed to decay of highly vibrationally excited ground state molecules formed by radiationless transfer from the ¹A₂ state. Similarities and differences with the results of previous studies of the H + pyrrolyl products arising in the UV photodissociation of pyrrole are discussed in terms of the likely nuclear motions on the relevant ground and excited PESs (along R_N–CH3/R_N–H), and the possible couplings between these surfaces. The present study confirms that the proposed model of ¹πσ^* state induced bond fission in heteroaromatic molecules [A.L. Sobolewski, W. Domcke, Chem. Phys. 259 (2000) 181] is also applicable to non-hydride substituted heteroaromatics, but that mass effects can have an important influence on the subsequent nuclear dynamics.     

The dependence of photoinduced energy transfer on the orientation of the acceptor with respect to the π-plane of the donor in naphthalene-linked crown ether–Tb complexes

The photoinduced energy transfer (ET) from naphthalene (N) to Tb³⁺ has been studied in the complexes of Tb³⁺ ion with 2,3-naphtho-17-crown-5 ether(I), 2,3-naphtho-20-crown-6 ether(II), 1,8-naphtho-21-crown-6 ether(III) and 1,5-naphtho-22-crown-6 ether(IV), respectively, using nitrate (NO₃⁻) ion as the counter anion in EtOH glass at 77 K. The ligands are so designed that the Tb³⁺ ion can be complexed with a predetermined orientation with respect to the naphthalene molecular plane. In systems I and II, the Tb³⁺ ion is along the Z-axis; in system III, it is along the Y-axis and in IV, it is along the X-axis, where Z- and Y- are the molecular in-plane long and short axes of the naphthalene molecular plane respectively and X- is the out-of plane axis perpendicular to the naphthalene molecular plane. Present studies indicate that the efficiency of energy transfer (ET) and the quenching of naphthalene phosphorescence show a strong dependence on the orientation of the acceptor metal ion (Tb³⁺) with respect to the π-plane of the donor naphthalene moiety. The ET studies suggest that an exchange mechanism involving the lowest (ππ^*) triplet state of N and the ⁵D₄ state of Tb³⁺ ion is predominantly operating. Our observation further indicates that for a given orientation in a complex the emission intensity of the various transitions (⁵D₄ → ⁷F_J, J=2–6) for Tb³⁺, vis-a-vis ET efficiency varies considerably with ΔJ values (=0, +1 and +2).     

Sulfur in different chemical surroundings – S K XANES spectra of sulfur-containing heterocycles and their quantum-chemically supported interpretation

The excited states in the XANES region of 2-mercaptobenzooxazole and 2-mercaptobenzothiazole and of their sulfur-bridged dimeric analogues were investigated at the sulfur 1s-ionization threshold by means of synchrotron radiation. The electronic excitations were treated employing density functional theory calculations. The theoretical results obtained for the planar monomers and the bent dimers are in good accordance with the experimental spectra. They allow the assignment of the spectral structures in the region of the S 1s-electron binding energy to π^* and σ^* resonances involving orbitals of the >C=S and –C–S_x–C– (x=1,2) moieties of the molecules. The results are discussed in terms of antibonding π^* and σ^* interactions between the sulfur and the neighboring carbon atoms and of the symmetric and antisymmetric combinations of the respective σ^* orbitals of the monomeric units.     

Measurement of atomic L shell fluorescence (ω1, ω2, ω3) and Auger (a1, a2 and a3) yields for some elements in the atomic number range 59≤Z≤85

A comprehensive set of theoretical Coster–Kronig and fluorescence yields are presented for atomic numbers 18≤Z≤100. These quantities are based on ab initio relativistic calculations. Agreement with experimental values is fair for ω₁ and generally good for ω₂, ω₃ (Z≥54) [1]. Therefore, atomic L shell fluorescence (ω₁, ω₂, ω₃) and Auger yields (a₁, a₂ and a₃) for some elements in the atomic number range 59≤Z≤85 were determined. These selected measured semi-empirical values were also fitted by least squares to polynomials in the Z of the form ∑_na_nZⁿ and compared with theoretical and with earlier fitted values.     

The effect of a positive charge on a π → π-transition

The position of the maximum for the π → π^*-transition of a bicyclic ketone containing a quaternary nitrogen atom at 3·1 Å from an :β-unsaturated ketone system is shown to depend largely upon electrostatic (repulsion) destabilization in both ground and excited states, the latter being affected more strongly.     

Observation and rovibrational analysis of the ν2 band of HCN–HCl

The high-resolution infrared absorption spectrum of an equilibrium mixture of HCN and HCl in a static gas long-path absorption cell is recorded in the 2500–2900 cm⁻¹ spectral region at 205 K. The spectrum shows rovibrational structure which has the typical appearance of a parallel band of a linear molecule and is assigned to the intramolecular H–Cl stretching vibration band ν₂ of the linear HCN–H³⁵Cl heterodimer. The rovibrational analysis of the band yield a band origin ν₀ of 2779.0968(12) cm⁻¹ together with a value for the upper-state rotational constant B′ of 0.067722(2) cm⁻¹. The observed red shift of 107 cm⁻¹ for the ν₂ band of HCN–H³⁵Cl relative to the H–Cl stretching vibration band of monomer H³⁵Cl is in excellent agreement with results from the MP2/6−311++G** level of theory. The value of the upper-state rotational constant shows that the intermolecular hydrogen bond shortens by 0.022 Å upon intramolecular vibrational excitation of the ν₂ mode.     

C CP MAS NMR, FTIR, X-ray diffraction and PM3 studies of some N-(ω-carboxyalkyl)morpholine hydrohalides

N-(ω-carboxyalkyl)morpholine hydrochlorides, OC₄H₈N(CH₂)_nCOOH·HCl, n=1–5, were obtained and analyzed by ¹³C cross polarization (CP) magic angle spinning (MAS) NMR, FTIR and PM3 calculations. The structure of N-(3-carboxypropyl)morpholine hydrochloride (n=3) has been solved by X-ray diffraction method at 100 K and refined to the R=0.031. The crystals are monoclinic, space group P2₁/c, a=14.307(3), b=9.879(2), c=7.166(1) Å, β=93.20(3)°, V=1011.3(3) ų, Z=4. In this compound the nitrogen atom is protonated and two molecules form a centrosymmetric dimer, connected by two N⁺–HCl⁻ (3.095(1) Å) and two O–HCl⁻ (3.003(1) Å) hydrogen bonds. ¹³C CP MAS NMR spectra, contrary to the solution, showed non-equivalence of the ring carbon atoms. The PM3 calculations predict a molecular dimer without proton transfer for an HCl complex, while for an HBr complex an ion pairs with proton transfer, and reproduces correctly the conformation of both dimers but overestimates H-bond distances. Shielding constants calculated from the PM3 geometry of ion pairs gave a linear correlation with the ¹³C chemical shifts in solids.     

Diphenylbutadiene-bridged gadolinium complex [GdCl2(THF) 3]2(μ-Ph2C4H4) · 3THF: The synthesis and crystal structure

The diphenylbutadiene-bridged gadolinium complex [GdCl₂(THF)₃]₂(μ-Ph₂C₄H₄) · 3THF (1) has been obtained by the reaction of Gd(III) chloride with diphenylbutadienepotassium. The molecular structure of 1 was determined by X-ray diffraction. The complex 1 has a binuclear structure in which a bridging diphenylbutadiene ligand is η⁴-bonded to the Gd atoms connecting two GdCl₂(THF)₃ units. Both Gd atoms have a distorted octahedral environment. At the Gd atom the two Cl atoms are in trans positions and the four other coordination sites are occupied by the three O atoms of THF molecules and the η⁴-bonded C₄H₄ fragment of a diphenylbutadiene ligand. In the two η⁴-bonded GdC₄H₄ fragments one of the Gd-C η⁴-distances is significantly elongated (2.86(3) and 2.97(3) Å) compared with other three (2.65(3)–2.69(3) and 2.67(3)—2.77(3) Å). The magnetic moment of Gd, equal to 8.1 BM, is typical for Gd³⁺ compounds that is evidence for a formal charge of DPBD ligand of −2 in complex 1. However, the expected distribution of the C-C bond of the diene fragment as long—short—long is not realized.     

One-electron wavefunctions. Accurate expectation values

Accurate expectation values for the total energy, the kinetic energy, the potential energy and the quadrupole moment integrals <X²> and <Z²> are calculated using the exact wavefunctions for the Isσ and 2pσ_u states of H⁺₂. A method has been developed to determine which regions of the wavefunction contribute most to a given expectation value.     

Synthesis and X-ray crystal structures of rac- and meso-2,2′-propylidene-bis(1-indenyl) zirconium dichlorides

An improved synthesis of 2,2′-bis(1-indenyl)propane and the corresponding ansa-complexes of zirconium are reported. Synthesis of a mixture of rac- and meso-2,2′-propylidene-bis(1-indenyl)zirconium dichlorides involves a treatment of ZrCl₄ with bis[3-(trialkyltin)inden-1-yl]propane, where alkyl = ethyl, butyl, in toluene. This reaction gives the products in 92% yield and might be a convenient synthetic pathway to a number of straightforward ansa-metallocenes. Both rac- and meso-2,2′-propylidene-bis(1-indenyl)zirconium dichlorides were separated and isolated using simple work-up processes, and characterized by X-ray crystal structure analysis (rac:C2/c; a = 15.903(3) Å, b = 11.105(2) Å and c = 11.520(2) Å; β = 121.61(3)°; Z = 4; V = 1732.6(5) ų; R = 0.0350; meso-: P1¯; a = 9.739(2) Å, b = 12.798(4) Å and c = 15.322(4) Å; = 101.18(2)°; β = 121.61(2)°; γ = 90.54(2)°, Z = 4; V = 1795.4(8) ų; R = 0.0417).     

Interactive n→σ delocalizations that control an aqueous organic equilibrium

Hydrated acetaldehydes were condensed in D₂O with substituted alcohols and thiols to determine ΔG of hemiacetalization by ¹H NMR. Specific n→σ^* delocalizations in the alkoxy/alkylthio functionality of the product interact to influence n→σ^* delocalization in the hemiacetal functionality. Delocalization in the latter functionality controls ΔG.     

Hydrogenmaleato bridged supramolecular double chains via π–π stacking interactions: syntheses, crystal structures and magnetic properties of ∞[Cu(phen)X(HL)2/2] with X=Cl (1), NO3 (2) and H2L=maleic acid

Two novel hydrogen maleato (HL) bridged Cu(II) complexes _∞¹[Cu(phen)Cl(HL)_2/2] 1 and _∞¹[Cu(phen)(NO₃)(HL)_2/2] 2 were obtained from reactions of 1,10-phenanthroline, maleic acid with CuCl₂·2H₂O and Cu(NO₃)₂·3H₂O, respectively, in CH₃OH/H₂O (1:1 v/v) at pH=2.0 and the crystal structures were determined by single crystal X-ray diffraction methods. Both complexes crystallize isostructurally in the monoclinic space group P2₁/n with cell dimensions: 1 a=8.639(2) Å, b=15.614(3) Å, c=11.326(2) Å, β=94.67(3)°, Z=4, D_calc=1.720 g/cm³ and 2 a=8.544(1) Å, b=15.517(2) Å, c=12.160(1) Å, β=90.84(8)°, Z=4, D_calc=1.734 g/cm³. In both complexes, the square pyramidally coordinated Cu atoms are bridged by hydrogen maleato ligands into 1D chains with the coordinating phen ligands parallel on one side. Interdigitation of the chelating phen ligands of two neighbouring chains via π–π stacking interactions forms supramolecular double chains, which are then arranged in the crystal structures according to pseudo 1D close packing patterns. Both complexes exhibit similar paramagnetic behavior obeying Curie–Weiss laws χ_m(T−θ)=0.414 cm³ mol⁻¹ K with the Weiss constants θ=−1.45, −1.0 K for 1 and 2, respectively.     

Interaction between a σ bond and a d MLn fragment: an MO analysis of the MnSiH three-center interaction in CpMnL2HSiR3 complexes

Two types of interactions between a σ bond and a dⁿ Ml_n entity are generally considered: in the first type the σ bond is complexed to the metal atom, acting as a 2-electron ligand; in the second type, an oxidative addition reaction occurs, leading to a complex in which the σ bond is broken. The two different complexes resulting from two kinds of interactions can often be considered as two isomers. Extended Hückel calculations on compounds of the type CpMnL₂HSiR₃ show that the three center MnHSi interaction can be viewed as belonging to the first type, i.e. a σ H---Si bond coordinated to the d⁶ CpMnL₂ fragment. Generalization for other dⁿ L_nMHSiR₃ complexes suggests that, when the H---bond is fully broken, the addition is not oxidative and that the bonding is better described as having a formally H⁻ and a formally SiR₃⁺ ligand coordinated to a metal atom which has the same formal oxidation state as in the free Ml_n fragment. The known experimental studies on these complexes are analysed on the basis of this MO analysis.     

Predicted radiolysis yield in a Fricke solution irradiated with various heavy ions

Experimental data on the spatial distribution of the energy deposited around an energetic heavy ion, from 1 MeV proton to 5.9 MeV/n uranium ion, which have been reported in the literature were documented to obtain a scaled radial dose distribution; (β/Z*)² D(Z*, β,t)=200 (for t=0–1), 200/t² (for t=1t_c), and 200 t_c/t³ (for t>t_c) where Z* and β are the effective charge and velocity relative to c, the velocity of light, of the incident ion, respectively, D the dose in unit of Gy, t the radial distance in unit of nm, t_c the critical distance empirically determined.

Then, if we know the yield of any chemical reaction as a function of dose from the results of experiments using γ-radiations or fast electrons or theoretical calculations, we can calculate the probability for the yield of the chemical reaction in the system bombarded with a heavy ion of the effective charge Z* and velocity β. The results of the present calculation of the LET-values and of G(Fe³⁺) in the ferrous sulfate acidic solution are presented and compared with reported experimental results.