Isotope effects on vibronic coupling of pyrazine

The vibronic couplings of pyrazine-d₀ and pyrazine-d₄ between the lowest electronic excited states ¹B_3u(n, π^*) and ¹B_2u(π, π^*) through the out-of-plane CH bending vibration ν_10a(b_1g) have been studied from the Raman, electronic absorption and fluorescence spectra. The isotope effects on the scattering cross section of the ν_10a Raman line, the vibrational potential in the ¹B_3u(n, π^*) state and on the frequency change of the ν_10a vibration between the ground and the lowest electronic excited states are well explained by conventional Herzberg-Teller coupling mechanism. However, the intensities of the vibronic bands in the electronic absorption and fluorescence spectra are hardly explained with this coupling mechanism.     

Electronic and vibronic spectra of Pr in LiYF4

The polarized absorption and fluorescence spectra of Pr³⁺ in single crystals of LiYF₄ having the scheelite structure have been investigated and assignments made on the basis of S₄ site symmetry. Strong vibronic coupling associated with the ³H₄→³H₅, ¹D₂ transitions in absorption and the ³P₀→³H_4,6 transitions in fluorescence was observed. Using selection rules for vibronic coupling and the known k = 0 phonons, these “extra” features of the spectrum can be accounted for in polarization and frequency.     

Tetraphenyltetrahydroporphin fine-structural vibronic spectra

Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 51, No. 4, pp. 609–614, October, 1989.     

Influence of spin-orbit coupling on vibronic spectra of metalocomplexes porphin: Manifestation of out-of-plane vibrations

In fine-structure phosphorescence spectra of metallocomplexes of porphin with ions of the Pd(II) and Pt(II) and their meso-deuterated derivatives additional lines have been detected which have no analogs in fluorescence and resonance Raman spectra of metalloporphyrins and in phosphorescence spectra of metallocomplexes of porphin with light ions of the Mg(II) and Zn(II). For Zn-porphin, quantum-chemical calculations of frequencies and forms of in-plane and out-of-plane vibrations have been performed. Based on experimental data and calculation results it has been found, that in vibronic phosphorescence spectra of metallocomplexes of porphin, out-of-plane gerade modes of the E _g symmetry (D _4h symmetry group) are manifested. The activity of out-of-plane vibrations increases with enhancing spin-orbital coupling upon changing to heavier chelated metal ions. Vibronic transitions with participation of out-of-plane gerade E _g vibrations manifest in the T ₁ → S ₀ transition through the vibronic intensity borrowing from the triplet-triplet ³ E _u -³ E _g transition.     

Role of vibronic coupling and of conformational substate distribution in determining the features of copper-protein EPR spectra

It is stressed that the presence of a metal ion directly bound to a protein can introduce elements of complexity, such as vibronic coupling, which cannot be ruled outa priori. As a typical example, two copper proteins, azurin and plastocyanin, have been considered. Electron paramagnetic resonance spectra of the two proteins, recorded in the range 4–200 K and with different cooling rates, support the hypothesis of a prominent role played by vibronic interactions as well as by the conformational substate distribution.     

Theory of optical spectra of impurity centres in crystals: general consideration of quadratic vibronic coupling

A method is proposed for the calculation of the spectra of the multiphonon transitions caused by the quadratic vibronic coupling with a phonon continuum. In the method, the time evolution of the final state is described by the path integrals. By applying the Stratonovich-Hubbard identity, the quadratic coupling is presented as the fluctuating linear coupling; the latter is calculated by the Lax method. As a result, the problem is reduced to the calculation of the determinants of matrices, the elements of which are given by the pair correlation functions of the contributing configurational coordinates. The method has been verified for the case of two mixed modes. Numerical calculations have also been made for a modified Debye model.     

Single vibronic level fluorescence spectra of sulfur dioxide

Single vibronic level fluorescence spectra of sulfur dioxide have been recorded throughout most of the region corresponding to the $\text{A}\text{?}\text{-}\text{X}\text{?}$ absorption. These spectra show progressions in the symmetric stretching mode of at least five members. Twelve origins between 30 972 and 31 776 cm^?1 show remarkably similar Franck-Condon (FC) patterns for this progression. Seven origins between 31 840 and 32 257 cm^?1 show another distinct FC pattern. This behavior is repeated for three more regions of excitation, each with a different distinct FC pattern and each containing numerous origins spread throughout a region of about 700 cm^?1. The progressions in the symmetric bending mode are essentially absent in the lowest energy excitation spectra and then slowly increase in length as the excitation energy increases. There is limited activity in both even and odd quanta of the antisymmetric stretching mode. These results are interpreted in terms of the levels of a zero-order ¹B₁ electronic state (with zero-order origin at around 31 240 cm^?1) that are very strongly vibronically coupled to many more ¹A₂ levels (with lower energy zero-order origin). The bulk of the emission is what would be expected from the zero-order ¹B₁ levels spread among the ¹A₂ levels.     

Factors governing the vibronic spectra of lanthanide compounds

Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 56, No. 2, pp. 183–191, February, 1992.     

Anharmonic resonances in the vibrational spectra of pyrazine

The quartic force field of pyrazine has been calculated in the B3LYP/6-31G(d) hybrid density-functional approximation. Based on the results of this calculation, the total IR (250–3800 cm^–1) and Raman (400–3200 cm^–1) spectra of pyrazine have been interpreted with consideration for the Fermi and Darling-Dennison resonances and their spectral manifestations. A precision method is proposed for anharmonic analysis of the vibrational states of polyatomic molecules on the basis of consideration of their theoretical anharmonicity constants in combination with the corresponding experimental frequencies. The method of linear scaling of frequencies has been theoretically substantiated.__________Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 1, pp. 13–22, January–February, 2005.     

Investigation of lattice dynamics by means of vibronic spectra

Electronic transitions at a foreign probe ion in a lattice exhibit vibrational sidebands. They may be used as a new tool to investigate lattice dynamics. To make this too effective the theory of vibronic spectra has been refined. The principal refinement is that of a partial Born-Oppenheimer approximation which establishes a rigid coupling of the electronic wavefunctions of the foreign ion to its own nucleus. The structural form of the one-phonon sideband is given as a projection of the classical Greens' function (imaginary part) onto single multipole-fields in lattice space. Employing a variety of electronic transitions and by careful group-theoretical analysis a complete irreducible sequence of projections can be extracted from the experiments. These functional forms depend sensibly on the eigenvectors of the lattice modes, whence they contain information, which cannot be received from neutron scattering. Moreover, the spectra related to the higher multipoles give insight into the disturbed (local) dynamics, whereas the lower type spectra concern the undisturbed (ideal) one. Systems, where the foreign probe ion has high symmetry, are most suitable for the new method. For systems of low local symmetry approximations are suggested by the low-frequency behaviour of the measured one-phonon band. Because of the high resolution of optical measurements, the information from vibronic spectra is comparable or even superior in detailed richness to neutron scattering data.     

Charge transfer excitons: dynamic theory of vibronic spectra

The vibronic spectra of charge transfer excitons (CTE) in a molecular one-component or alternatingly ordered two-component chain are treated in the framework of a dynamic approach (neglecting thermal excitations of the intramolecular vibrations). The model introduces two mechanisms of coupling between CTEs and vibrational quanta: (1) shift of the equilibrium positions of the nuclei in the ionized donor or acceptor; (2) change of the vibrational frequency in the ionized molecule. This model allows to generalize the simple CTE Hamiltonian and the vibronic Hamiltonian of Frenkel excitons. The linear optical susceptibility is calculated in the vibronic region (one CTE and one vibrational quantum). The double splitting of vibronics of CTEs was analyzed: (1) the splitting connected with the location of the intramolecular vibration on the donors or on the acceptors; (2) the splitting connected with the symmetry of the vibronic spectra (in the degenerate case). The general structure of the vibronic spectra of CTEs is established. It contains structureless absorption lines, which correspond to two-particle bands (the phonon is excited on a neutral molecule neighboring the donor or the acceptor) and Lorentz-type lines of one-particle states, which correspond to the bound propagation of the CTE and the phonon.     

Resonant channel coupling in electron scattering by pyrazine

Detailed investigation of the three low-energy resonances seen in electron scattering by the diazabenzene molecule pyrazine reveals that the first two are nearly pure single-channel shape resonances, but the third is, as long suspected, heavily mixed with core-excited resonances built on low-lying triplet states. Such resonant channel coupling is likely to be widespread in pi-ring molecules, including the nucleobases of DNA and RNA, where it may form a pathway for radiation damage.     

Isotopic effect in the vibronic spectra of europium compounds

The effect of the kinematic factor on vibronic spectra of europium compounds and Eu³⁺-doped lanthanide compounds was examined experimentally. It was demonstrated that isotopic or quasi-isotopic substitution of the ions of the crystal lattice gives rise not only to the changes of the vibration frequencies but also to alteration of the value of electron-phonon interaction. The latter displays in changing the relative integral intensity of vibronic sidebands of electronic transitions of Eu³⁺ ion. Eu³⁺ vibronic spectra of a number of pairs of natural and isotopically or quasi-isotopically substituted compounds: nitrates, halides, formates, acetates, oxalates, β-diketonates, etc., were studied. In most cases the substitution of deuterium for hydrogen was applied. Decrease of the electron-phonon interaction with the increase of the isotopic mass depends on different structural characteristics. It was found that a factor of decreasing the relative intensity of the vibronic sideband of electronic transition of Eu³⁺ ion lies within the range ∼1.2 and ∼7 for pairs of compounds under investigation. The largest change of the intensity of vibronic sidebands was observed in a pair of formates Eu(HCOO)₃ and Eu(DCOO)₃ having the tridentate-bridging coordination of the formate anions and a three-dimensional frame structure. One should take into consideration both decreasing the vibration frequencies and diminishing the value of electron-phonon interaction at introduction of heavy isotope or quasi-isotope in the crystal lattice of lanthanide compounds to reduce the multiphonon quenching of luminescence.     

Resonance Raman profile with consideration for quadratic vibronic coupling

A relation is found between the first-order Raman profile and the absorption spectrum of a scattering centre with regard to the quadratic vibronic coupling in a zero-temperature case. Two non-degenerate electronic states of the centre are considered, the adiabatic and Condon approximations are used, and the vibrations of the centre are assumed to be harmonic.     

Some expected anomalies in the impurity vibronic spectra of ferroelectrics

The influence of the soft phonon branch on some characteristics of the impurity vibronic absorption spectra in ferroelectrics is qualitatively analyzed and illustrated using simple models. The following quantities are discussed: the intensity, the temperature shift and the half width of the no-phonon line, the one-phonon wing, the integral intensity of a parity forbidden band. It is shown that near the phase transition point (T > T_c) all these characteristics must show anomalous dependencies on temperature, if compare with usual matrix crystals. The observation of “plateaus” may be expected in these dependencies. Various aspects of obtaining information from measured impurity vibronic spectra of ferroelectrics are discussed.