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71.
A. P. Popov N. S. Shelekhov O. V. Bandyuk O. B. Ratner T. M. Vember A. O. Rebezov G. I. Lashkov 《Theoretical and Experimental Chemistry》1986,22(2):219-224
Sensitized photooxidation of a series of compounds with an anthracene structure in a block poly(methyl methacrylate) (PMMA) containing a tetrapyrrole pigment (TPP) or anthraquinone dyes as spectral sensitizers, was studied. The values of changes in the molar refraction at equal to 441 and 633 nm were determined experimentally. They satisfactorily agreed with the theoretical values calculated from dispersional relationships. The initial quantum yields of the photooxidation (0ox) of the anthracene compounds were measured both in solution and in PMMA blocks. The lack of correlation between the 0ox values in the solid polymers and in the liquid solution indicates the dominating role of the polymeric matrix in determining the effectiveness of photooxidation process taking place. In the selection of the optimal polymerization conditions for the synthesis of the polymeric blocks, the values of 0ox of certain anthracene compounds can be up to 1. In the series of the anthraquinone dyes used, 1,4-dihydroxy and 2-aminoanthraquinones, whose 0ox reaches the values of 0.2–0.25 have the highest sensitizing ability.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 22, No. 2, pp. 235–240, March–April, 1986. 相似文献
72.
I. V. Komarov A. V. Turov S. V. Popov Yu. L. Slominskii M. Yu. Kornilov 《Theoretical and Experimental Chemistry》1991,27(2):179-182
It was established by PMR with lanthanide shift reagents that the charge in anionic cyanine dyes with a linear chromophore is concentrated at the ends of the polymethine chain, while in compounds containing a vinylene group in the chromophore it is concentrated in the region of the five-membered ring. The results are compared with the data from13C NMR spectroscopy and relaxation measurements in the presence of Gd(fod)3. The validity of the conclusions is also considered.Kiev University. Institute of Organic Chemistry, Academy of Sciences of the Ukrainian SSR, Kiev. Translated from Teoreticheskaya i Éksperimental'naya, Vol. 27, No. 2, pp. 197–201, March–April, 1991. Original article submitted December 20, 1989. 相似文献
73.
Kaledin AL 《The Journal of chemical physics》2005,122(18):184106
A formulation of a direct, iterative method for obtaining the lowest eigenvalues and eigenvectors of a Hessian matrix is presented. Similar to the iterative schemes in electronic structure configuration interaction calculations (methods due to Lanczos, Davidson, and others), the mass-weighted Hessian matrix K is not constructed explicitly; instead, its operation on a basis vector (a direction in the 3N Cartesian configuration space of the atoms) is computed based on the principles of dynamical equations of motion. By noting that the time derivative of the gradient vector in the harmonic force field is related to the particles' momenta via dg/dt = Kp, a Hessian-vector product can be computed on the fly by finite differentiation of the gradient along the direction specified by the p vector. Thus, only two evaluations of the gradient are required per Davidson-like iteration per root, which leads to a linear scaling behavior of the computational effort with the number of atoms (provided that the evaluation of the gradient scales linearly). Preliminary results are presented for a 27,000-atom 4He nanodroplet. 相似文献
74.
Dr. Alexey S. Kiryutin Mikhail S. Panov Dr. Alexandra V. Yurkovskaya Prof. Dr. Konstantin L. Ivanov Prof. Dr. Geoffrey Bodenhausen 《Chemphyschem》2019,20(5):766-772
A study of long-lived spin order in chlorothiophene carboxylates at both high and low magnetic fields is presented. Careful sample preparation (removal of dissolved oxygen in solution, chelating of paramagnetic impurities, reduction of convection) allows one to obtain very long-lived singlet order of the two coupled protons in chlorothiophene derivatives, having lifetimes of about 130 s in D2O and 240 s in deuterated methanol, which are much longer than the T1-relaxation times (18 and 30 s, respectively, at a field =9.4 T). In protonated solvents the relaxation times become shorter, but the lifetime is still substantially longer than . In addition, long-lived coherences are shown to have lifetimes as long as 30 s. Thiophene derivatives can be used as molecular tags to study slow transport, slow dynamics and slow chemical processes, as has been shown in recent years. 相似文献
75.
It has been suggested [F. H. Stillinger, J. Chem. Phys. 112, 9711 (2000)] that the convergence or divergence of M?ller-Plesset perturbation theory is determined by a critical point at a negative value of the perturbation parameter z at which an electron cluster dissociates from the nuclei. This conjecture is examined using configuration-interaction computations as a function of z and using a quadratic approximant analysis of the high-order perturbation series. Results are presented for the He, Ne, and Ar atoms and the hydrogen fluoride molecule. The original theoretical analysis used the true Hamiltonian without the approximation of a finite basis set. In practice, the singularity structure depends strongly on the choice of basis set. Standard basis sets cannot model dissociation to an electron cluster, but if the basis includes diffuse functions then it can model another critical point corresponding to complete dissociation of all the valence electrons. This point is farther from the origin of the z plane than is the critical point for the electron cluster, but it is still close enough to cause divergence of the perturbation series. For the hydrogen fluoride molecule a critical point is present even without diffuse functions. The basis functions centered on the H atom are far enough from the F atom to model the escape of electrons away from the fluorine end of the molecule. For the Ar atom a critical point for a one-electron ionization, which was not previously predicted, seems to be present at a positive value of the perturbation parameter. Implications of the existence of critical points for quantum-chemical applications are discussed. 相似文献
76.
T. M. Zubareva T. M. Prokop’eva I. V. Kapitanov I. A. Belousova N. G. Razumova A. F. Popov 《Theoretical and Experimental Chemistry》2007,43(4):247-254
Neutral forms of hydroxylamine, N-methylhydroxylamine, and N,N-dimethylhydroxylamine are typical α-nucleophiles in water.
In comparison with aryl anions of similar basicity their rate of reaction in the decomposition of 4-nitrophenyl diethylphosphonate
is increased by about 102 times. Decomposition of the substrate is accelerated in cetyltrimethylammonium bromide micelles (about 4 to 30 fold). Hydroxylamine
and its N-alkyl derivatives are the most effective low basicity nucleophiles. The sole factor responsible for the micellar
effects is the concentration of the reagent in the surfactant micelles.
__________
Translated from Teoreticheskaya i éksperimental’naya Khimiya, Vol. 43, No. 4, pp. 231–236, July–August, 2007. 相似文献
77.
L. D. Popov Yu. P. Tupolova S. I. Levchenkov V. V. Lukov V. A. Kogan 《Russian Journal of Coordination Chemistry》2007,33(3):208-212
A series of novel mono-and binuclear copper(II) complexes with substituted salicylaldehyde acylhydrazones H2L of the formula CuL · xH2O (x = 0 and 1) and [Cu(HL)](ClO4)(CH3OH) were synthesized. The isolated dimeric complexes of copper acetate were found to exist as isomers with different bridging atoms. In dimers showing a superexchange between the paramagnetic centers through bridging phenoxide O atoms, the antiferromagnetic exchange couplings were much stronger than those in complexes with bridging O atoms of the a-oxyazine fragment. 相似文献
78.
Krause M Popov VN Inakuma M Tagmatarchis N Shinohara H Georgi P Dunsch L Kuzmany H 《The Journal of chemical physics》2004,120(4):1873-1880
Metal-carbon cage vibrations of crystalline endohedral D2d-M2@C84 (M=Sc,Y,Dy) dimetallofullerenes were analyzed by temperature dependent Raman scattering and a dynamical force field model. Three groups of metal-carbon cage modes were found at energies of 35-200 cm(-1) and assigned to metal-cage stretching and deformation vibrations. They exhibit a textbook example for the splitting of molecular vibrations in a crystal field. Induced dipole-dipole and quadrupole-quadrupole interactions account quantitatively for the observed mode splitting. Based on the metal-cage vibrational structure it is demonstrated that D2d-Y2@C84 dimetallofullerene retains a monoclinic crystal structure up to 550 K and undergoes a transition from a disordered to an ordered orientational state at a temperature of approximately 150 K. 相似文献
79.
Sharutin V. V. Pakusina A. P. Egorova I. V. Platonova T. P. Bukvetskii B. V. Popov D. Yu. 《Russian Journal of Coordination Chemistry》2002,28(12):827-830
Tetraphenylantimony nitrite was synthesized by reacting pentaphenylantimony with triphenylantimony dinitrite at a molar ratio of 1 : 1 in toluene, and its structure was determined using X-ray diffraction analysis. The Sb atom is coordinated to the oxygen atom of the axial nitrite group to form a trigonal bipyramid. The Sb–C(Ph)eq distances vary within the 2.103–2.111(3) Å range, and the S–O(1) and Sb–C(41) bond lengths are equal to 2.386(3) and 2.156(3) Å, respectively. The Sb...N distance and the axial C(41)SbO(1) angle are equal to 3.133(4) Å and 174.7(1)°, respectively. 相似文献
80.
I. I. Popov A. M. Simonov S. N. Kolodyazhnaya 《Chemistry of Heterocyclic Compounds》1970,6(11):1463-1465
3-(1-Methyl-2-benzimidazolyl)acrylic acid was obtained by the reaction of 1,2-dimethylbenzimidazole with chloral and subsequent hydrolysis of the condensation product. The hydrochloride of the chloride of this acid and its esters and amides were synthesized. The methyl and ethyl esters of the acid were synthesized by the Wittig reaction. The IR and UV spectra of the compounds obtained are presented.See [9] for Communication XXIV.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1566–1568, November, 1970. 相似文献