Effect of Deuteration on Quasiline Electronic‐Vibrational Spectra of Phthalocyanine

Quasiline electronicvibrational spectra of fluorescence and absorption (excitation of fluorescence in selective recording) of the molecules of phthalocyanine deuterated around the periphery of benzene rings (H₂Phcd ₁₆) and the center of the macrocycle (D₂Phc) are obtained. The vibrational frequencies of the ground state are almost insensitive to this deuteration (except for vibrations with the participation of angular deformations). In excitation spectra, changes in deuteration are more pronounced due to the effects of nonadiabatic vibronic interaction of the vibrational sublevels of the S ₁ state and of the purely electronic level S ₂.     

Amplification Coefficient of the Anti‐Stokes Component of Raman Scattering

The theory of intracavity parametric interaction of the components of Raman scattering is developed in the prescribedintensity approximation, which takes into account the reverse reaction of the excited waves to the pumpingwave phase. It is shown that one can substantially improve the conversion efficiency or the amplification coefficient of the antiStokes component by selection of the intracavity geometry, the optimum phase relation between the interacting waves, the pumping level, and the phase mismatch.     

The Order Parameter and Phase Transformations in Compounds with Ionic Stoichiometry

The paper considers instability of a symmetric linear ion chain against a spontaneous distortion that orders ions of opposite charge without a multiple change in the spacing. Transverse deformation in dense chains is observed. The dipolar interaction responsible for 3D ordering of similar structures of Cu—O chains in yttrium perovskites has been assessed. The superclose ion packing in Cu—O chains is explained by the existence of an oriented hole orbital in the electronic structure of bivalent copper. The possible role of this orbital as an additional degree of freedom leading to thermodynamic singularities at intermediate temperatures below the tetra–ortho transition temperature has been investigated.     

A new strategy for the design of water-soluble synthetic receptors: specific recognition of DNA intercalators and diamines

Water-soluble zinc bisporphyrin receptors 1 and 2 having two Lewis acidic sites (zinc) in the hydrophobic environment consisting of alkyl chains and a bisporphyrin framework, and covered with hydrophilic exterior (twelve or eighteen carboxyl groups) were prepared. The receptors show high affinity for diamines and DNA intercalators in water where the binding constants K(a) are of the order of 10(7) and 10(8) M(-1), respectively. Diamines and DNA intercalators are bound to the receptor through different mechanisms. Diamines are bound through hydrophobic interactions and zinc-nitrogen interactions, while DNA intercalators are bound through hydrophobic interactions and charge-transfer interactions. Flexible alkyl chains can make van der Waals contact with guests and create a hydrophobic environment around the bound guest by an induced-fit-type mechanism. For the binding of DNA intercalators, the following features are noteworthy: 1). Binding constants are similar between the zinc porphyrins and zinc-free porphyrins; 2). the binding constant is larger for the guest having the lower LUMO; this indicates the important contribution of charge-transfer interactions to binding; 3). the hydrophobic and cationic nature of DNA intercalators is substantially important, and 4). higher ionic strength reduced the binding affinities; this shows a moderate contribution of electrostatic interactions. The conformational instability of the receptors also contributes to the tight binding: hydrophobic and electrostatic interactions cannot both be favorable at the same time in the guest-free receptor. Enthalpy-entropy compensation observed for the binding of diamines and DNA intercalators is characterized by a relatively small slope (alpha=0.74) and a large intercept (beta=7.75 kcal mol(-1)) in the DeltaH degrees versus TDeltaS degrees plot; this shows that a conformational change of receptors and a significant desolvation occur upon binding. The receptor can competitively bind to propidium iodide to deprive DNA of the intercalated propidium iodide. These features of water-soluble receptors consisting of a rigid framework and flexible side chains with a large solvent-accessible area are in contrast to highly preorganized rigid receptors, and they can provide useful guidelines for rational design of induced-fit artificial receptors in water.     

Nuclear hyperfine coupling interactions in the rotational spectra of the linear and bent isomers of HF-N2O

The rotational spectra of six isotopomers of the linear and bent isomers of HF-N₂O have been collected in the 7-18 GHz region with a Fourier transform microwave spectrometer. The nuclear hyperfine structure in the spectra produced by HF spin-spin coupling interaction and nuclear quadrupole coupling interactions due to the D nucleus of DF and the nuclei of N₂O have been resolved and analyzed. In the linear isomer, H in HF is bonded to the terminal N in N₂O. The NF bond lengths are 2.9808(2) Å for the HF-containing isotopomers and 2.9732(2) Å for the DF-containing isotopomers. The zero point angles are 23.1° for HF and 31-34° for N₂O. The hyperfine constants suggest that the HF bond is lengthened by 0.0105 Å upon complexation and that the electric field gradients of the two nitrogen nuclei in N₂O are perturbed differently in the complex. In the bent isomer, the hydrogen bond is formed between HF and O in N₂O. The intermolecular distances are 3.4942(2) Å for the HF-containing isotopomers and 3.4436(2) Å for the DF-containing isotopomers, with HF and N₂O forming angles of 34° and 46°, respectively, with the intermolecular axis. The nuclear quadrupole coupling constants of the two nitrogen nuclei do not indicate electric field gradient perturbation in this isomer.     

A rotation-torsion-vibration treatment with three-dimensional internal coordinate approach and additional FTIR spectral assignments for the CH3-bending fundamentals of methanol

A theoretical model has been developed to account for certain features of both newly observed and previously reported CH₃-bending subbands between 1450 and 1570 cm⁻¹ in the high-resolution Fourier transform infrared spectrum of CH₃OH [Can. J. Phys. 79 (2001) 435]. The features include (i) an apparent inversion of the rotationless E-A torsional splitting with respect to the ground state, i.e., the A state located above the E state, (ii) a pronounced upward slope in the K-reduced torsion-vibration energy pattern for the subband origins, and (iii) unexpected A₁/A₂ inversion of the K=2A and K=3AJ-rotational levels that led to ambiguity in identifying the vibrational mode as or . The model is an effective internal coordinate Hamiltonian constructed in G₆ molecular symmetry with the CH₃-bends coupled to each other and to torsion and including a- and γ-type Coriolis coupling. With this model, 33 out of 36 experimental upper-state K-term values for newly assigned , and ν₁₀ subbands plus previous ν₄ subbands have together been fitted successfully, employing 9 adjustable parameters and 17 fixed parameters to give a standard deviation of 0.14 cm⁻¹. The P_γ Coriolis term appears to be the leading cause of the upward shift in the K-reduced energies. When J-dependence is introduced via a rotational Hamiltonian including b- and c-type Coriolis terms in addition to molecular asymmetry, the observed A₁/A₂ inversion of the K=2A and 3A rotational levels can also be reproduced. Predictions using the fitted K-rotation-torsion-vibration Hamiltonian show an interesting Coriolis-induced crossover and mixing of the ν₅ and ν₁₀ torsion-vibration energy patterns. These predictions played a role in identifying two of the new ν₅ subbands in the crossing region, thereby helping to validate the model.     

The Impact of the Phenyl Spacer on the Electronic Structure and Spectra of Porphyrin Dimers

Quantum-chemical investigation of the electronic structure and properties of the excited states of porphyrin dimers, in which monomeric subunits are linked by the phenyl spacer, is performed by semiempirical methods. The molecular orbitals of the monomeric subunits are shown to interact with each other via molecular orbitals of the phenyl ring. Comparison of the experimental absorption data and quantum-chemical calculations of electronic absorption spectra for different conformations of Zn-tetraphenylporphyrin dimer is performed and the main conformation of the dimer in a solution at 295 K, in which the planes of tetrapyrrole macrocycles are located at an angle of about 60°, is substantiated.     

Jahn–Teller coupled charge density wave in a double exchange system

In a two orbital model, we formulate Jahn–Teller coupled charge density wave in one electron per lattice site limit. Softening of Jahn–Teller phonons corresponding to distortion modes Q₂ or Q₃ associated with perfect nesting of Fermi surface leads to this instability at low temperature. The gap equation for charge density wave state and its dependences on electron–lattice coupling are calculated explicitly when any one of the Jahn–Teller modes is excited cooperatively. We find that the Q₂ distortion mode yields lowest free energy. Effect of electron–lattice interaction on collective mode, such as amplitude mode, is more pronounced when the excited mode is Q₂.     

Angle-resolved photoemission spectroscopy study of Fe(1 1 0) single crystal: Many-body interactions between quasi-particles at the Fermi level

A high-resolution angle-resolved photoemission spectroscopy (ARPES) study of Fe(1 1 0) single crystal was conducted to elucidate many-body interactions between quasi-particles at the Fermi level at low-temperature. Two kink structures were observed in the energy-band dispersion at the binding energies of ∼40 meV and ∼270 meV for the bulk-derived band on the majority-spin Fermi surface around the Γ point. Based on analyses of the experimentally obtained real parts of the self-energy, these kink structures are derived from electron-phonon and electron-magnon interactions.     

A representation of the polarization term in the interaction energy between a molecule and a point-like charge

The interaction energy of a molecule M with a point-like charge q can be partitioned into simpler contributions, two of which can be expressed in terms of the charge distribution _M of the sole M. The first term, qV(r), represents the interaction of q with the undistorted charge _M ⁰ of M while the second q ² P(r) gives the additional contributions due to the polarization of _M ⁰ under the influence of the charge q placed at the point r. In this paper we investigate the possibility of getting an inexpensive and sufficiently accurate analytical representation of P(r) over the whole space outside the van der Waals volume of M.