Методом вакуумного співосадження атомів міді і молекул С60 одержано тонкі гранульовані плівки нанокомпозита С60–Cu ізвмістом Cu 80 ат.%, 34 ат.% та 8 ат.%. Ці плівки відпалювали при температурі 473 К протягом 10, 20, 30 годин у вакуумі. Для плівок з меншим вмістом атомів міді вже після осадження спостерігається різке зменшення відносної інтенсивності та розширення дипольно активної у раманівському розсіянні коливної моди Ag(2), чутливої до перенесення зарядів від атомів металу до С60. З відпалом зменшення її інтенсивності супроводжується зростанням інтенсивності і розширенням смуги коливної моди Нg(8). Крім того, з відпалом зростає інтенсивність триплетного випромінювання. Аналогічні процеси, але із запізненням, відбуваються у гранульованій плівці з більшим вмістом атомів міді. Трансформація спектрів коливань і фотолюмінесценції вказує на полімеризацію та руйнування молекул С60, яке відбувається за рахунок дифузії атомів міді з гранул у середовище С60 з подальшим встановленням між ними хімічної взаємодії за рахунок перенесення зарядів від атомів металу до фулеренів.

Роботу виконано в рамках молодіжної науково-дослідної роботи 16БФ051-02М Міністерства освіти і науки України.

The article summarizes a number of quantum-chemical and spectral studies of the electron structure and the nature of electron transitions in neutral cyanine bases, compared to their parent cationic cyanines. The authors consider series of symmetrical indocyanines, unsymmetrical pyrido-thiacyanines and thia-styryls with donor and acceptor substituents, all of them with corresponding bases. A difference in the electron structure and spectral properties between the bases and their parents is established despite their both having closed pi-electron shells. Quantum-chemical calculations show that the bond lengths in the polymethine chains of bases are alternated similarly to polyenes, whereas the bond lengths in cationic cyanines are equalized, even in unsymmetrical dyes. The characteristic alternation of atomic charges in cationic cyanines decreases upon going to cyanine bases. Therefore, the latter are typical donor-acceptor linear conjugated systems. Going from the cationic dye to the base, electron levels are notably shifted and the energy gap is increased. The long-wavelength band in the absorption spectrum shifts hypsochromically, becomes wider and more nuanced; this effect is caused by the vibrational transitions, but not by the second electron transition. A specific n-MO also appears at the two-coordinated atom in the acceptor residue of the base, along with a n -> pi* electron transition, not present in cations. The calculated properties of cyanine bases are in a good agreement with the experimental NMR and absorption spectrum data. Overall, both quantum-chemical and spectral studies show that the observed features of cyanine bases are largely determined by the electronic and geometrical structure of these compounds as polyenic conjugated molecules.

Influence of high energetic electron irradiation (E-e = 1.8 MeV) on the vibration properties of the squaraine dye film was studied. Quantum-chemical calculations were applied for determination of vibration bands in Raman spectra of the squaraine dye molecule. Results of Raman scattering of the film showed that its irradiation with dose of 1 MGy leads to shift of vibration bands positions by 2 ... 6 cm(-1), appearance of background due to knocking of the atoms from the squaraine dye molecules. But all vibration modes at this dose are still present that points on possibility of functioning of the squaraine film in solar elements at this dose.

Results of thin fullerite C-60 films irradiation with Fe+ ions, energy of which is E = 140 k.V and doses varied from 1.2.10(12) t. 0.66.10(14) ions/cm(2) are considered. Raman spectroscopy and XRD data show that after irradiation of fullerenes C-60 with Fe+ ions dimmers and polymers with orthorhombic and tetragonal structures are formed that is similar to phases formed under high temperatures and pressure. At highered doses polymerized phases disappear because of destruction and formation of amorphous phase.

New non-linear quantum concepts on the influence of vibrational resonances sequences and strong vibrational-electronic interactions and unstable chemical structures are developed on the basis of vibrational spectroscopy and quantum chemical calculations of fullerenes C-12(60), (C12C59)-C-13, (C2C58)-C-13-C-12, BNC58 et al., complexes with metal atoms C60M. Increase in the splitting and frequency shifts of the vibrational bands, as well as the increase in the intensity of active and "dumb" vibrations in the resonance vibrations of C-60 Hg(3,7) (2Hg(3)approximate to Hg(7)) was established which is due to the influence of the non-linear resonant interaction of vibrations.

This paper presents the results of spectral measurements of UV–Vis absorption and 13C NMR spectra as well as quantum-chemical studies of molecular geometry and electron structure of squaraine, thiosquaraine and their corresponding 1,2-isomers. In the ground state 1,3- and 1,2-isomers have similar charge distributions and bond lengths within their chromophores but differ substantially in energy gap sizes and spectral properties, most prominently the maxima positions and intensities of long wavelength absorption bands. The replacement of oxygen atoms connected to the central cycle in squaraine with less electronegative sulfur atoms evokes a relatively intensive band in the short wavelength spectral region.

Influence of high-energetic Ti+ ions (E-i = 140 keV) irradiation on C-60 fullerite film and on radiation-stimulated phase transitions was studied by methods of X-rays diffraction and Raman spectroscopy. XRD pattern and Raman spectrum prove that even at low fluences of 1,2.10(12) ions/cm(2) appear new phases: orthorhombic, tetragonal and rhombohedral that coexist with initial face-centered cubic phase. Lattice parameters of these phases change with increase of the fluence denoting that interstitial Ti ions promote appearance of donor-acceptor interaction, magnitude of which depends on conditions of irradiation. At the fluence of 0,66.10(14) ions/cm(2) not only polymerization but destruction of molecular cages is observed due to increase of radiation damages.

Thin granulated films of C60–Cu nanocomposite with the Cu contents of 80, 34, and 8 at.% were fabricated with the use of the vacuum codeposition method. The films were annealed at a temperature of 473 K for 10, 20, and 30 h in vacuum. Films with lower Cu contents demonstrated a drastic relative intensity decrease and a broadening of the Ag(2) dipole-active vibrational band in the Raman spectrum, which is sensitive to the charge transfer from metal atoms to C60 molecules. Further annealing was accompanied not only by a decrease of this band intensity, but also by an intensity increase and a broadening of the Hg(8) vibrational mode band. Moreover, annealing gave rise to the growth of the triplet radiation emission intensity. Similar processes, but with some delay, also occurred in a granular film with a higher copper content. The transformation of Raman and photoluminescence spectra evidenced the polymerization and the destruction of C60 molecules owing to the diffusion of copper atoms into C60 crystallites, followed by the chemical interaction between those two components due to the charge transfer from metal atoms to fullerenes.

Results of thin fullerite C-60 films irradiation with Fe+ ions, energy of which is E=140 keV and doses varied from 1,2x10(12) to 0,66x10(14) ions/cm(2) are considered. Raman spectroscopy and XRD data show that after irradiation of fullerenes C-60 with Fe+ ions dimmers and polymers with orthorhombic and tetragonal structures are formed that is similar to phases formed under high temperatures and pressure. At highered doses polymerized phases disappear because of destruction and formation of amorphous phase.