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41.
Anna Painelli Francesca Terenziani Zoltán G. Soos 《Theoretical chemistry accounts》2007,117(5-6):915-931
We discuss electron-transfer processes that govern the physics of several materials or systems of interest for advanced applications.
The discussion touches upon several topics, ranging from solvatochromism to solvent-induced symmetry breaking, from excitonic
to cooperative effects in molecular crystals, from phase transitions to vibrational contributions to the dielectric constant
in organic materials, from spectroscopy to molecular transport. In all these diverse systems electron transfer (ET) plays
a major role and is discussed with reference to simple models for delocalized charges. 相似文献
42.
R. Acevedo T. Meruane E. Cortés S. O. Vasquez C. D. Flint 《Theoretical chemistry accounts》1994,88(2):99-110
Summary A theoretical model to calculate the vibronic intensities induced by the odd vibrational modes in centrosymmetric lanthanide complexes is developed and applied to octahedral complex ions, LnX
6
3–
, such as occur in the hexachloroelpasolites Cs2NaLnCl6. Both the crystal field and the ligand polarisation contributions are evaluated using a standard set of symmetry coordinates. For the crystal field term a truncated expansion of the intermediates states is employed rather than the more conventional closure approximation. Special care is necessary to ensure that the phases of the contributions are correctly determined since the cross-term between the ligand polarisation and crystal field contributions is signed. General equations applicable to anyf
n
complex ion are derived and an example of their application to the PrCl
6
3–
ion is given The agreement with experiment is satisfactory. 相似文献
43.
Daniel M. Chipman 《Theoretical chemistry accounts》1989,76(2):73-84
Summary The suitability of Gaussian basis sets for ab initio calculation of Fermi contact spin densities is established by application to the prototype first-row atoms B-F having open shell p electrons. Small multiconfiguration self-consistent-field wave functions are used to describe relevant spin and orbital polarization effects. Basis sets are evaluated by comparing the results to highly precise numerical grid calculations previously carried out with the same wave function models. It is found that modest contracted Gaussian basis sets developed primarily for Hartree-Fock calculations can give semiquantitative results if augmented by diffuse functions and if further uncontracted in the outer core-inner valence region. 相似文献
44.
45.
Summary The calculation of the effects of temperature and isotopic composition on the energy weighted moments of the dipole oscillator strength distribution of H2 in the random phase approximation to the polarization propagator are reported. It is seen that the effect of isotopic composition is small, while that of temperature is of an order accessible to experiment. We find that all the mean excitation energiesI
, for =–1, 0, 1, decrease with temperature as does the dipole oscillator strength momentS() for >0, while the opposite is true for <0. These effects are interpreted in terms of the bond length dependence of the excitation energies. 相似文献
46.
C. Etzlstorfer H. Falk N. Müller T. N. H. Tran 《Monatshefte für Chemie / Chemical Monthly》1996,127(6-7):659-668
Summary PPP type semiempirical quantum chemical calculations of absorption spectra were performed for hypericin, fringelit D, stentorin, and their respective conformers, tautomers, and deprotonated species. The results agree with the experimental absorption spectra of hypericin, stentorin, and fringelit D, their deprotonated species, and the polarized absorption spectra of an ,-long chain appended hypericin derivative embedded in stretched polyethylene.
Strukturelle Aspekte und elektronische Absorptionseigenschaften der Hydroxyphenanthroperylenchinone Fringelit D, Hypericin und Stentorin
Zusammenfassung Semiempirische quantenchemische Rechnungen (PPP-Typ) der Absorptions-spektren von Hypericin, Fringelit D, Stentorin und ihrer Konformeren, Tautomeren und deren Deprotonierungsprodukten wurden durchgeführt. Die Resultate stehen in Einklang mit den experimentellen Absorptionsspektren von Hypericin, Fringelit D, Stentorin, ihrer Deprotonierungsprodukte und dem polarisierten Absorptionsspektrum eines in gestrecktem Polyethylen eingebetteten ,-substituierten Hypericinderivates.相似文献
47.
This paper reports voltammetric sequential determination of Pt(II), Pd(II), and Rh(III), by square-wave adsorption stripping voltammetry (SWAdSV), and Pb(II), by square-wave anodic stripping voltammetry (SWASV), in vegetable environmental matrices. Analytical procedures were verified by the analysis of the standard reference materials: Olive Leaves BCR-CRM 062 and Tomato Leaves NIST-SRM 1573a. Precision and accuracy, expressed as relative standard deviation and relative error, respectively, were always less than 6% and the limits of detection (LOD) for each element were below 0.096 g g–1. Once set up on the standard reference materials, the analytical procedure was transferred and applied to laurel leaves sampled in proximity to a superhighway and in the Po river mouth area. A critical comparison with spectroscopic measurements is discussed. 相似文献
48.
H. Kienitz 《Angewandte Chemie (International ed. in English)》1969,8(10):733-750
The important advances being made in modern analytical methods are indicative of the fundamental changes that are occuring in the theory and practice of “analytical chemistry”. “Information optimization” demands a new approach in teaching and research, and calls for the intergration of chemistry with other scientific and technical disciplines. 相似文献
49.
John D. Watts Miroslav Urban Rodney J. Bartlett 《Theoretical chemistry accounts》1995,90(5-6):341-355
Summary This paper reports a series of coupled-cluster (CC) calculations through CCSDT on the theoretically challenging ground state of the BeO molecule. Along with CC methods, quadratic configuration interaction (QCI) approximations to CC theory have been used (QCISD and QCISD(T)), which show several dramatic failings. Equilibrium electrical properties (,
xx
, and
zz
) and basic spectroscopic properties (r
e, e,D
e, and infrared intensity (I)) have been computed. Basis set and electron correlation effects are analyzed in order to arrive at accurate values of the dipole moment and polarizability, which are not known experimentally. For the dipole moment, we obtain a value of 6.25 D, with an uncertainty of about 0.1 D. For
xx
and
zz
, we suggest respective values of 32 and 36 atomic units (a.u.) and error bars of about 1 and 2 a.u. With extended basis sets, the spectroscopic propertiesr
e, e, andD
e are reproduced to high accuracy, which is the first time this has been achieved for this species byab initio methods. At the highest calculation levels,I is predicted to be very small. AlthoughI has not been measured, some support for this prediction comes from a recent infrared study of BeO-rare gas complexes. The QCI methods are shown to be much more sensitive to basis set, and even with large basis sets yield values of
zz
andI which differ from CC results by an order of magnitude and three orders of magnitude, respectively. These differences doubtless arise from the importance of single excitations (T
1) for this molecule, as several terms involvingT
1 are neglected in the QCISD approximation compared with CCSD. We also report CC calculations with Brueckner orbitals, which yield results similar to those obtained with restricted Hartree-Fock orbitals. 相似文献
50.
Xiao-Xiang Li Jun-Wen Wang Yu-Jing Guo Ling-Hong Kong Jing-Hao Pan 《Journal of inclusion phenomena and macrocyclic chemistry》2007,58(3-4):307-315
In phosphate buffer solution of pH5.4, the interaction of meso-tetrakis(2-thienyl)porphyrin(H2TTP) and Cu-meso-tetrakis(2-thienyl)porphyrin(Cu-TTP) with α-cyclodextrin(α-CD), β-CD, γ-CD, heptakis(2,3,6-tri-O-methyl)-β-CD(TM-β-CD)
has been studied by means of UV-vis, fluorescence and 1HNMR spectroscopy, respectively. The H2TTP and Cu-TTP can form 1:2 inclusion complexes with TM-β-CD and 1:1 inclusion complexes with the other three cyclodextrins.
In this paper, the inclusion constants (K) of H2TTP and Cu-TTP for the formation of the inclusion complexes have been estimated from the changes of absorbance and fluorescence
intensity in phosphate buffer solution. The inclusive capabilities of different kinds of cyclodextrins are compared. The result
shows that the inclusion ability of α-CD with H2TTP and Cu-TTP is the strongest among the three native CDs. The inclusion ability of modified β-CD with H2TTP and Cu-TTP is stronger, compared to the native β-CD, which indicates that the capacity matching plays a crucial role in
the inclusion procedure except for the hydrophobic effect. In addition 1HNMR spectra supports the inclusion conformation of the TM-β-CD-Cu-TTP inclusion complex, indicating the interaction mechanism
of inclusion processes. 相似文献