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** Local gauge invariance symmetry **

** Symmetry Exploitation in Local MP2 Method for Periodic Systems **

** Symmetry molecular orbitals, local **

** Symmetry of Localized Crystalline Orbitals. Wannier Functions **

Solid state NMR is a relatively recent spectroscopic technique that can be used to uniquely identify and quantitate crystalline phases in bulk materials and at surfaces and interfaces. While NMR resembles X-ray diffraction in this capacity, it has the additional advantage of being element-selective and inherently quantitative. Since the signal observed is a direct reflection of the local environment of the element under smdy, NMR can also provide structural insights on a molecularlevel. Thus, information about coordination numbers, local symmetry, and internuclear bond distances is readily available. This feature is particularly usefrd in the structural analysis of highly disordered, amorphous, and compositionally complex systems, where diffraction techniques and other spectroscopies (IR, Raman, EXAFS) often fail. [Pg.460]

Next come the dihedral angles (or torsions), and the contribution that each makes to the total intramolecular potential energy depends on the local symmetry. We distinguish between torsion where full internal rotation is chemically possible, and torsion where we would not normally expect full rotation. Full rotation about the C-C bond in ethane is normal behaviour at room temperature (although 1 have yet to tell you why), and the two CH3 groups would clearly need a threefold potential, such as... [Pg.40]

With respect, to a local symmetry plane, the basic orbitals are either <7,, symmetric or antisymmetric. This is true not only for the... [Pg.3]

CC and CH bond orbitals but also for the CTL, ami CH3 group orbitals. If the local symmetry elements are preserved in the full molecule, the 7r (or a) local orbitals can combine to give v (or o) molecular orbitals. The reader should, therefore, not be surprised to find, for instance, tt type molecular orbitals in cyclopropane which are delocalized over the CH2 groups. [Pg.3]

In molecules with little or no symmetry, it may still be possible to recognize the main localized-orbital component of certain molecular orbitals. It is then convenient to adopt the label of this localized type as the label of the molecular orbital, even though the molecular symmetry does not coincide with the local symmetry. For instance, in methylenimine again, the 5A orbital is clearly built out of the in-plane 7rc 2 group orbital, with a small NH component. We therefore label the orbital t CU2, although the molecule does not have a vertical symmetry plane. Similarly, the orbitals 7A and 8A of propylene are labeled 7TqH3, tt CU2 (111.49).a Other examples where the local symmetry is sufficiently preserved and only weakly perturbed by the molecular environment are hydrazine (111.34) and methylamine (III.31). In some cases we have omitted the label as no unambiguous classification is possible. [Pg.53]

The axial resonance is assigned to ruthenium A with its D4h local symmetry (compare gj = 2.51, gy = 1.64 in traw.s-RuCl4(PEt3)J) while the rhombic signal is assigned to ruthenium B , where the local symmetry is D2h and three different components of the g-tensor are expected. [Pg.32]

Recognize molecular symmetry planes and axes. Even approximate, or local symmetry elements may be useful. One should not step back just because, formally, the molecule has no symmetry elements. A methyl and an ethyl substituent, or chlorine and bromine substituent, can be equated. Substituents that disrupt the molecular symmetry but have trivial electronic requirements may be deleted. [Pg.6]

The structure of the [Fe2 / - 82) P o - 61148) )2] complex is presented in Figure 1. The structure we used was obtained from x-ray crystallography, symmetrized such that the environments of the two Fe atoms are the same. The local symmetry of each Fe atom is C3, the overall symmetry of the complex is Ci. To aid in the interpretation of the computed results we oriented the complex such that the z-axis passes through the center of mass and the projections of the two P — Fe- 8 line segments onto the z-axis are maximized. [Pg.358]

There is one other factor contributing to the overall symmetries of the lattice structure. This factor involves the local symmetry of the atomic groups which actually form the structure. Examples are the "solid-state building blocks" given above, e.g.- the tetrahedon - the group, P043-, and... [Pg.55]

Based on the experience with tertiary phosphines, the importance of the steric properties of NHC hgands in determining chemical behaviour has been immediately recognised. The main practical problem, however, is that NHC hgands substantiaUy present a local symmetry axis, whereas phosphines present a local symmetry axis. This imphes that the well-accepted molecular descriptor used to quantify steric properties in phosphines, the Tohnan cone angle [78], cannot be applied to NHC ligands. [Pg.16]

B2) 888 (Aj) methyl groups in transposition assignment acc. to local symmetry C21,. Compounds with higher alkyl substance are known, too (43)... [Pg.72]

It can be understood as one Aj and one Bj mode, assigned on the basis of a local symmetry 78). In comparison to free ethyl acetate, the CO stretching frequency of which lies at 1742 cm 104), this band is shifted by about 50 cm by Mn-0 bonding. [Pg.75]

In a conventional Fe Mossbauer experiment with a powder sample, one would observe a so-called quadrupole doublet with two resonance lines of equal intensities. The separation of the lines, as given by (4.36), represents the quadrupole splitting The parameter Afg is of immense importance for chemical applications of the Mossbauer effect. It provides information about bond properties and local symmetry of the iron site. Since the quadrupole interaction does not alter the mean energy of the nuclear ground and excited states, the isomer shift S can also be derived from the spectrum it is given by the shift of the center of the quadrupole spectrum from zero velocity. [Pg.93]

Ga( Zn)silicon The two-electron acceptor impurity of Zn is present in silicon only in the form of neutral (ZnO) or doubly ionized Zn centers depending on the Fermi-level position. Broadening of the spectra corresponding to the above centers indicates that the local symmetry of these centers is not cubic... [Pg.268]

Ga( Zn), Sn, Te( I) Mossbauer spectroscopy, no modifications of the local symmetry of lattice sites, electronic structure of atoms and intensity of electron-phonon interaction are revealed for Pbi Sn Te solid solutions in the gapless state at 80 and 295 K... [Pg.269]

Along the local symmetry axis of a n- or pseudo-tt orbital (with a+H interacting with the Tt-density) when B carries no n-pairs, or... [Pg.34]

Assuming that a reasonable force field is known, the solution of the above equations to obtain the vibrational frequencies of water is not difficult However, in more complicated molecules it becomes very rapidly a formidable one. If there are N atoms in the molecule, there are 3N total degrees of freedom and 3N-6 for the vibrational frequencies. The molecular symmetry can often aid in simplifying the calculations, although in large molecules there may be no true symmetry. In some cases the notion of local symmetry can be introduced to simplify the calculation of vibrational frequencies and the corresponding forms of the normal modes of vibration. [Pg.123]

A hysteresis cycle in the molar susceptibility measurements has been observed for [Ni2(Medpt)2(N3)2(/r-N3)2] (883). This has been ascribed to a phase transition caused by an asymmetrization process of the rhombus-like centrosymmetric [Ni-(N3)2-Ni] core that occurs with falling temperature. The asymmetrization transition can be explained in terms of a second-order Jahn-Teller distortion, taking into account the local symmetry of the dinuclear [Ni-(N3)2-Ni] entity (D2h, rhombic symmetry) before the arrangement.2128... [Pg.466]

One of the interesting consequences of changing specifications is the effect on the equation structure. With formulations C and D, the occurrence matrix is symmetric. But if external flows, w, and model parameters, / , are introduced as the unknown variables, the symmetry may be destroyed. One way of preserving the local symmetry is to augment the system of equations and to bifurcate the variables in terms of state and design variables (M2). [Pg.146]

See also in sourсe #XX -- [ Pg.80 ]

See also in sourсe #XX -- [ Pg.596 , Pg.597 ]

See also in sourсe #XX -- [ Pg.102 ]

** Local gauge invariance symmetry **

** Symmetry Exploitation in Local MP2 Method for Periodic Systems **

** Symmetry molecular orbitals, local **

** Symmetry of Localized Crystalline Orbitals. Wannier Functions **

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