The Interaction Vector Model and the Intensity of the Secondary Transition of the Benzene Chromophore in Strained Natural Molecules: Sesamol,Melacacidin, Tetrahydropapaverolin,Renifolin, Pterocarpin,Peltogynol

A method (the New Vector Model : NVM) designed to approach the intensity of the secondary transition of the benzene chromophore with-CH3 and-OR substituents, has been recently published ¹ This method is based on MNDO calculations. It has been applied to strained chromophores with fused rings, ² assuming that it is possible to take into account the incidence of strain on intensity in introducing a strain vector in the vector scheme used to calculate the transition moment vector. In another step it has been derived a much simpler method which avoids the quantum calculations. It can be brought into play using graphically simple vector addition rules. ³ This method is based on a new concept : the interaction vector (underneath, the method is called the Interaction Vector Model : IVM). It has been designed to study alkyl and-OR substituents, since we are mainly involved in the study of natural products and many natural products display such substituents. This IVM has not been designed to take into account the perturbations induced by the strain on intensity. The present work is devoted to the adaptation of the IVM to strained benzene chromophores. It is given several examples on the way it can be used on strained natural molecules.     

Assignment of pre‐edge peaks in K‐edge x‐ray absorption spectra of 3d transition metal compounds: electric dipole or quadrupole?

The characteristics of pre‐edge peaks in K‐edge x‐ray absorption near edge structure (XANES) spectra of 3d transition metals were reviewed from viewpoints of the selection rule, coordination number, number of d‐electrons, and symmetry of the coordination sphere. The contribution of the electric dipole and quadrupole transition to the peaks was discussed on the basis of the group theory, polarized spectra, and theoretical calculations. The pre‐edge peak intensity for T_d symmetry is larger than those for O_h symmetry for all 3d elements. The intense pre‐edge peak for tetrahedral species of 3d transition metals is not due to 1s–3d transition, but transition to the p component in d–p hybridized orbital. The mixing of metal 4p orbitals with the 3d orbitals depends strongly on the coordination symmetry, and the possibility is predictable by group theory. The transition of 1s electron to d orbitals is electric quadrupole component in any of the symmetries. The d–p hybridization does not occur with regular octahedral symmetry, and the weak pre‐edge peak consists of 1s–3d electric quadrupole transition. The pre‐edge peak intensity for a compound with a tetrahedral center changes as a function of the number of 3d electrons regardless of the kind of element; it is maximized at d⁰ and gradually decreases to zero at d¹⁰. The features of pre‐edge peaks in K‐edge XANES spectra for 4d elements and the L₁‐edge for 5d elements are analogous with those for 3d elements, but the pre‐edge peak is broadened due to the wide natural width of the core level. Copyright © 2008 John Wiley & Sons, Ltd.     

π-Electron Densities in Molecules ΦCHX1X2 and Correlation with the Intensity of the 00 Band of the Secondary Transition

In molecules such as ΦX₁X₂X₃the intensity of the secondary transition of the benzene chromophore, strongly depends on long range interactions involving a σ·π coupling between orbitals belonging to the C_α-X bonds, and the πΦ system. Such a coupling distorts the symmetry of the π_Φ system(1–5). The secondary transition (towards 260 nm) which is forbidden when the symmetry is D_6h - as in the benzene molecule itself where only the low intensity progression A isobserved - becomes all the more allowed as the substituent is able to distort the πΦ cloud towards a C_2V symmetry. A new progression called B is observed. Its intensity is usually evaluated by the measure of its 00 band. The distorsion of symmetry arises because of the π donating or π withdrawing electronic effects of the substituent(1–7). These phenomena have been explained on the ground of a V shaped function(l) : ε₀₀ = f(σ), where σ is a parameter linked to the electronic effects of the substituents. When the whole substituent is a π donating one, its π donating effect is lowered by an increase of the electron attracting power of the groups X : the perturbation of the D_6h symmetry is lessened and ε₀₀ decreases. On the contrary, when the whole substituent is a π withdrawing one, an increase of the withdrawing power of the groups X increases the withdrawing power of the whole substituent, the distorsion of the D6h symmetry increases and ε₀₀ increases too. The minimum of the V shaped curve correspond to the species for which the π donating tendency of the aliphatic part of the substituent is quenched by the electron withdrawing tendency of the groups X. The D_6h symmetry of the πΦ cloud is restored. The transition is forbidden and the system A only is observed.     

Structural features of the polymer-like phase of AC60 fullerides

A new approach is proposed for describing the deformation of the C₆₀ molecule in the polymer-like phase of the fullerides AC₆₀ (A=K, Rb). A discrete basis of orientational states of the molecule is introduced, and orientational ordering is described on the basis of a phenomenological theory. A symmetry analysis of the molecular vibrations in the Fm3m phase is performed. It is shown that small rotations of the C₆₀ can occur at a phase transition. Pis’ma Zh. éksp. Teor. Fiz. 64, No. 2, 110–115 (25 July 1996)     

Theoretical calculation of an external heavy-atom effect on the spin-orbit coupling of the benzene molecule

The mechanism of direct spin-orbit coupling arising from electrostatic interaction of the electrons on the perturbed molecule with the nuclei of the perturber is investigated theoretically for the case of benzene in the presence of external heavy atoms. Matrix elements are evaluated using Slater-type orbitals and the von Neumann expansion, and by using gaussian-type orbitals. Results of the present calculation confirm the experimental evidence (from polarization studies by Giachino and Kearns and phosphorescence measurements by Hofeldt, Sahai and Lin) that mixing by the perturber of the triplet state of the molecule with its singlet states is not the mechanism for introducing intensity into the radiative T ₁ - S ₀ transition.     

Orientational states of C60 molecule in crystals

Local symmetry of orientational states of the C₆₀ molecule in crystals has been investigated. It was shown that the various orientational phase transitions in different crystals are related to different orientational orbits. The model of orientational phase transitions based on a sequence of orientational states with different symmetry properties has been suggested. We have found that both the local symmetry of C₆₀ molecule and the symmetry of its internal vibrations become higher after a reduction of crystal spatial symmetry at the phase transition. This effect is fairly common and can be observed in the orientational order-disorder phase transitions with wave vectors at the Brillouin zone boundary. Feasible manifestations of the predicted effect in various experiments are discussed. Zh. éksp. Teor. Fiz. 113, 1081–1093 (March 1998)     

Intensity of the Secondary Transition of Some 1,3-Benzodioxole Derivatives

1,3-benzodioxole derivatives display a charge transfer (C.T.) transition n₀ → π^* _φ, involving the non-bonding electrons of the oxygen atoms (n₀ stands for the pπ orbitals of the oxygen atoms) and a π^* _φ orbital. It has been studied in a preceding paper for derivatives with a strongly perturbating subtituent: X, in para to one of the oxygen atoms (figure 1).¹ These derivatives will be named underneath Bzd-X (for example Bzd-CO₂H). In the present work, we want to study the intensity of the secondary transition which obeys to rules very different from those of the C.T. transition.     

A conceptual model for surface states and catalysis ond-band perovskites

This paper proposes a conceptual model to describe symmetry factors believed to be most important in catalyzing a reaction on a transition metal oxide. An hypothetical situation is constructed from a model reaction, the dimerization of ethylene to form cyclobutane, and a model perovskite, SrTiO₃. A detailed review is given of the symmetry imposed energy barrier for the gas phase reaction. Then it is shown how thed _xy, d_xz, d_yz atomic orbitals have the symmetry required to reduce this energy barrier when a transition metal atom is included in the reaction. It is also shown how the evergy barrier reduction depends upon the electronic occupation of thed orbitals and upon the relative energies of thed orbitals involved in the reaction. Using SrTiO₃ as an example, it is shown that the perovskites possess highly localized, atomic-liked surface states of the required symmetry. Two semiquantitative examples are developed for the catalyzed dimerization of ethylene on the (100) surface of SrTiO₃. A preliminary discussion is given of the role played by surface potentials in promoting the reaction.     

Microwave spectrum of tropone

The microwave spectrum of tropone (2,4,6-cycloheptatriene-1-one) has been obtained and assigned. The observation of a statistical weight intensity alternation indicates that the molecule has C_2v symmetry. Relative intensity measurements show the molecule to possess a low wavenumber vibration whose 1-0 interval is 60 ± 20 cm^?1. The dipole moment is found to be 4.1 ± 0.3 D by the “rate-of-growth” method.     

Spin polarization effect for Mn2 molecule

The density functional theory method （DFT） （b3p86） of Gaussian 03 has been used to optimize the structure of the Mn2 molecule. The result shows that the ground state of the Mn2 molecule is an 11-multiple state, indicating a spin polarization effect in the Mn2 molecule, a transition metal element molecule. Meanwhile, we have not found any spin pollution because the wavefunction of the ground state does not mingle with wavefunctions of higher-energy states. So the ground state for Mn2 molecule being of an 11-multiple state is the indicative of spin polarization effect of the Mn2 molecule among those in the transition metal elements： that is, there are 10 parallel spin electrons in a Mn2 molecule. The number of non-conjugated electrons is the greatest. These electrons occupy different spacious orbitals so that the energy of the Mn2 molecule is minimized. It can be concluded that the effect of parallel spin in the Mn2 molecule is larger than the effect of the conjugated molecule, which is obviously related to the effect of electron d delocalization. In addition, the Murrell-Sorbie potential functions with the parameters for the ground state and other states of the Mn2 molecule are derived. The dissociation energy De for the ground state of the Mn2 molecule is 1.4477 eV, equilibrium bond length Re is 0.2506 nm, vibration frequency ωe is 211.51 cm^-1. Its force constants f2, f3, and f4 are 0.7240 aJ·nm-2, -3.35574 aJ·nm^-3, 11.4813 aJ·nm^-4 respectively. The other spectroscopic data for the ground state of the Mn2 molecule ωeχe, Be, αe are 1.5301 cm^-1, 0.0978 cm^-1, 7.7825×10^-4 cm^-1 respectively.     

Polarization dependence of luminescence induced by two-photon excitation in LiF crystals with F 3 + laser color centers and the symmetry of the excited state

The energy level structure of F ₃ ⁺ laser color centers in crystals of LiF is discussed. A high-power laser (λ _ex=920 nm) is used to excite luminescence from LiF crystals with F ₃ ⁺ centers via two-photon absorption, and the dependence of the polarization and intensity of this luminescence on the polarization of the laser light is measured and calculated. It is shown that the two-photon transition involves the excitation of a previously unknown state of the F ₃ ⁺ center—a spin singlet whose wave function has ¹ A ₁ symmetry. Fiz. Tverd. Tela (St. Petersburg) 39, 1373–1379 (August 1996)     

Spin polarization effect of Ni2 molecule

The density functional theory （DFT） method （b3p86） of Gaussian 03 is used to optimize the structure of the Ni2 molecule. The result shows that the ground state for the Ni2 molecule is a 5-multiple state, symbolizing a spin polarization effect existing in the Ni2 molecule, a transition metal molecule, but no spin pollution is found because the wavefunction of the ground state does not mingle with wavefunctions of higher-energy states. So the ground state for Ni2 molecule, which is a 5-multiple state, is indicative of spin polarization effect of the Ni2 molecule, that is, there exist 4 parallel spin electrons in Ni2 molecule. The number of non-conjugated electrons is greatest. These electrons occupy different spatial orbitals so that the energy of the Ni2 molecule is minimized. It can be concluded that the effect of parallel spin in the Ni2 molecule is larger than that of the conjugated molecule, which is obviously related to the effect of electron d delocalization. In addition, the Murrell-Sorbie potential functions with the parameters of the ground state and other states of the Ni2 molecule are derived. The dissociation energy De for the ground state of the Ni2 molecule is 1.835 eV, equilibrium bond length Re is 0.2243 nm, vibration frequency we is 262.35 cm^-1. Its force constants f2, f3 and f4 are 1.1901 aJ.nm^-2, -5.8723 aJ.nm^-3, and 21.2505 aJ.nm^-4 respectively. The other spectroscopic data for the ground state of the Ni2 molecule ωeχe, Be and αe are 1.6315cm 2, 0.1141 cm^-1, and 8.0145× 10^-4 cm^-1 respectively.     

外电场作用下TiO光激发特性研究

利用密度泛函BLYP方法优化得到了TiO分子的稳定构型,并计算了TiO分子基态在外场作用下前线轨道变化情况,然后利用杂化组态相互作用CIS-DFT方法,比较了TiO分子在外电场下的激发特性.结果表明,在一定的电场范围内,随着电场的增大,α轨道的最高占据轨道与最低空轨道能隙逐渐变小,β轨道能隙逐渐变大,同时可跃迁的低激发态跃迁波长随电场的增大而变长,高激发态波长变化相对复杂,且基态跃迁至激发态的耦合强度随外电场的增大而加强.     

Photoelectron and electron impact spectrum of HCN

The electronic structures of HCN and DCN have been determined by examining high resolution He(I) photelectron spectra of HCN and DCN, He(II) photoelectron spectrum of HCN, and the electron impact energy loss spectra of HCN and DCN. The present investigation supports an earlier assignment of the orbital sequence in HCN. New vibrational data are presented and the Rydberg series and valence transitions are reinvestigated. The adiabatic ionization energies for the 1π and 5σ orbitals in HCN are found to be 13.607 ± 0.002 eV and 14.011 ± 0.003 eV respectively.As mentioned above the investigation of the Rydberg series indicated that the first IP at 13.607 eV is the 1π ionization and the second IP at 14.011 eV is the 5σ ionization. A comparison of the experimental and theoretical intensity ratio between the two first PES progressions also supports this assignment. It is further supported by the fact that in the second IP the ν₃ vibration frequency is not changed as much as it is in the first IP, which is in agreement with the PES of N₂ and CO. The analysis of the bending vibrations also supports this ordering of the orbitals.The same orbital assignment has recently been proposed by Frost et al.⁵, using a comparison with the HCP photoelectron spectrum. The present paper supports their assignment of orbitals and (00⁰0)-(00⁰0) transitions. There are, however, some disagreements concerning the vibrational analysis. This is probably due to the fact that the HCN spectrum of Frost et al.⁵ revealed less structure than ours. As indicated by Figure 5 there is possibly still more structure to be revealed.     

A theoretical interpretation of the abnormal D0→F4 intensity based on the Eu local coordination in the Na9[EuW10O36]·14H2O polyoxometalate

The Na₉[EuW₁₀O₃₆]·14H₂O polyoxometalate studied here has shown a peculiar 4f-4f emission spectrum that has two main differences in comparison to data reported previously in the literature: a ⁵D₀→⁷F₀ line with much smaller intensity and an abnormally high intensity of the ⁵D₀→⁷F₄ transition. These results have been theoretically interpreted in terms of the Ω_λ intensity parameters and their dependence on the nature and local symmetry of the chemical environment around the Eu³⁺ ion, leading to the conclusion that the chemical environment is highly polarizable with a local symmetry corresponding to a slightly distorted D_4d coordination geometry. Further evidences corroborating this interpretation were obtained by progressively dissolving the polyoxometalate in water, inducing a progressive accommodation of the coordination polyhedron towards lower symmetries.     

Electronic and electronic-vibrational phenomena in the new organic conductor ϰ-(ET)2[Hg(SCN)2Cl] with a metal-insulator transition

The reflection spectra and optical conductivity spectra of the new organic conductor ϰ-(ET)₂[Hg(SCN)₂Cl] with a metal-insulator transition in the spectral regions 700–5500 and 9000–40 000 cm⁻¹ have been studied in polarized light at 300 K. A comparisonis made between the spectra obtained and the corresponding spectra of related isostructural conductors based on the ET molecule, and also the properties of the crystal structure of the investigated compounds. An electronic transition between the ET molecules of the dimer (ET) ₂ ⁺ in the spectral region 700–5500 cm⁻¹ has been identified, as have the features of the electronic-vibrational structure arising as a consequence of the interaction of this transition with the completely symmetric intramolecular vibrations of the ET molecule. It is found that the conductor with the stronger dimer interaction between the ET molecules has the higher the transition temperature. Fiz. Tverd. Tela (St. Petersburg) 39, 1313–1319 (August 1997)     

Electronic Absorption Spectrum of Mesitylene Vapour

Abstract

The electronic absorption spectrum of mesitylene vapour has been photographed on a Q-24 Medium Quartz Spectrograph. The molecule belongs to D_3h symmetry and the transition is A→₁A₂ which is forbidden and due to that the (0,0) band does not appear in the spectrum. The position of (0,0) band in this case has been fixed at 36562 cm^?1 with the help of 0→1 and 1→0 transitions. There are 66 bands and most of them are assigned in terms of two ground state frequencies of magnitudes 278 and 519 cm^?1 and 7 excited state frequencies of magnitudes 267, 436, 554, 968, 1268, 1386 and 1575 cm^?1     

Localization in YBa2Cu3O7 induced by the self-interaction correction to the density functional theory

We address the question whether intra-atomic repulsion U in YBa₂Cu₃O₇ is strong enough to provide electron localization. We use a recently proposed self-interaction-correction (SIC) based approach which provides a qualitative criterion (symmetry breaking) for electron localization. Using a first-principle LMTO-Green-function technique we show that only d_xy, d_yz and d_zx orbitals of Cu in the CuO₂ plane get localized; localized orbitals have 4.5 eV smaller energy then itinerant ones (which gives an estimate of U). d_x²−y² and d_3z²−r² orbitals of Cu and p-orbitals of O are stable against localization.     

Temperature investigations of Raman spectra of stoichiometric and congruent lithium niobate crystals

In the temperature range 100–450 K, we have investigated Raman spectra of congruent and stoichiometric LiNbO₃ crystals. We have found that, in this temperature range, frequencies and widths of all the spectral lines depend linearly on temperature. However, the width of the line that corresponds to vibrations of the A₁(TO) symmetry of Li⁺ ions depends on temperature much more weakly than the width of the line that corresponds to vibrations of the A₁(TO) symmetry of Nb⁵⁺ ions. This fact indicates that the anharmonicity of vibrations of Nb⁵⁺ ions along the polar axis is much stronger compared to vibrations of Li⁺ ions. It is likely that this anharmonicity is noticeably contributed by O^2? ions, which are characterized by an anharmonic potential, vibrations of which, according to calculations from first principles, are mixed with vibrations of Nb⁵⁺ ions. The anharmonicity of vibrations of O^2? ions is evidenced by a strong temperature dependence of the width of the line that corresponds to vibrations of the A₁(TO) symmetry of O^2? ions perpendicularly to the polar axis. We have found that the temperature dependence of the intensity of lines that correspond to fundamental vibrations is nonmonotonic. At the same time, the temperature dependence of the intensity of “superfluous lines” is strictly linear. It is likely that this behavior of the intensities of lines of fundamental vibrations is related to the occurrence of clusters and microstructures in the crystal structure.     

Energy shifts and forbidden transitions in H+ 2 due to electronic g/u symmetry breaking

A full account is given of calculations and measurements of transition frequencies and intensities of the forbidden pure rotation transition (v = 19, N = 1)-(v = 19, N = 0) in the ground electronic state (1sσ_g) of H⁺ ₂. The transition has measurable intensity because of ortho-paru mixing that arises from electronic g/u symmetry breaking caused by the Fermi contact hyper-fine interaction. Measurements of the transition were made in both single and double resonance using a fast ion beam/microwave spectrometer. The transition frequency was determined to be at 14961.7 ± 1.1 MHz (95% confidence, 5 measurements), in excellent agreement with the theoretical prediction of 14960 ± 3 MHz. The intensity of the transition relative to the allowed 1sσ_g (v = 19, N = 1)-2pσ_u,(v = 0, N = 2) transition was estimated from the available measurements to be 8000, in reasonable agreement with the theoretically predicted value of ?3000.