Cluster quantum-chemical calculations

HZSM-5, 42 131, 133 of terminal hydroxyl groups, 34 147 Cluster quantum-chemical calculations to compare catalytic activities of BASs, 34 183... 

On Some Capacities of Cluster Quantum-Chemical Calculations in Comparing Specific Catalytic Activities of Different BASs of Aluminosilicates... 

Keywords Sulfur clusters Quantum-chemical calculations Stability Isomers Spectra... 

Good agreement between C(- and the dipole moment of the solvent (H20) molecules (i.e., by the hydrophilicity of metals) established by Trasatti25,31 was found and the reasons for this phenomenon were explained 428 The Valette and Hamelin data150 251 387-391 are in agreement with the data from quantum-chemical calculations of water adsorption at metal clusters 436-439 where for fee metals it was found that the electrode-H20 interaction increases as the interfacial density of atoms decreases. 

Water adsorption and dissociation on Ni( 111) and Nig(6 + 2) clusters have been studied by ab initio quantum-chemical calculations.744 "746... 

It is thus obvious that among numerous computational methods, first principles quantum chemical approach is indispensable. However, initially first principles quantum chemical calculations required the use of models consisting of a few atoms (clusters) and the range of properties was limited. Since the advent of modem computing resources, as well the models could be extended to cover larger variety of structures as the methodology has been... 

A structural classification of 8 is difficult due to the fact that an arrangement of metal atoms as in 8 is uncommon in the whole field of molecular metal clusters. For this reason, detailed understanding of the bonding properties in 8 requires quantum chemical calculations. Theoretical analysis seems to be especially applicable to learning more about the bond between the two tetrahedra, which appears at first to be an isolated metal-metal bond between two metal atoms in the formal oxidation state zero. 

The requirements for Raman resonance that must be fulfilled are the following (120,121) (a) total symmetry of the vibrations with respect to the absorbing center, and (b) same molecular deformation induced by the electronic and vibrational excitations. Quantum chemical calculations (41) of the vibrational frequencies and the electronic structure of shell-3 cluster models allowed the assignment of the main vibrational features, as shown in Fig. 7. The 1125 cm-1 band is unequivocally assigned to the symmetric stretching of the Ti04 tetrahedron. 

The existence of critical solvation numbers for a given process to happen is an important concept. Quantum chemical calculations using ancillary solvent molecules usually produce drastic changes on the electronic nature of saddle points of index one (SPi-1) when comparisons are made with those that have been determined in absence of such solvent molecules. Such results can not be used to show the lack of invariance of a given quantum transition structure without further ado. Solvent cluster calculations must be carefully matched with experimental information on such species, they cannot be used to represent solvation effects in condensed phases. 

Quantum Chemical Calculations on the Electronic Structure of Zeolite Clusters... 

Not all quantum chemical calculations on zeolite clusters involve necessarily millions of integrations, and in the case of iso-electronic chemical systems fulfilling certain geometrical criteria, almost trivial back-of-an-envelope type calculations can yield rigorous upper and lower energy bounds. Fortunately, some zeolite structural units fulfill these geometric criteria. 

Microwave spectroscopy is probably the ultimate tool to study small alcohol clusters in vacuum isolation. With the help of isotope substitution and auxiliary quantum chemical calculations, it provides structural insights and quantitative bond parameters for alcohol clusters [117, 143], The methyl rotors that are omnipresent in organic alcohols complicate the analysis, so that not many alcohol clusters have been studied with this technique and its higher-frequency variants. The studied systems include methanol dimer [143], ethanol dimer [91], butan-2-ol dimer [117], and mixed dimers such as propylene oxide with ethanol [144]. The study of alcohol monomers with intramolecular hydrogen-bond-like interactions [102, 110, 129, 145 147] must be mentioned in this context. In a broader sense, this also applies to isolated ra-alkanols, where a weak Cy H O hydrogen bond stabilizes certain conformations [69,102]. Microwave techniques can also be used to unravel the information contained in the IR spectrum of clusters with high sensitivity [148], Furthermore, high-resolution UV spectroscopy can provide accurate structural information in suitable systems [149, 150] and thus complement microwave spectroscopy. 

Infrared spectroscopy is the workhorse in this field, because it can quickly provide dynamical details, discriminate between different cluster sizes and phases [40], and sample a wide spectral range. It often yields valuable feedback for quantum chemical calculations. In contrast to some action spectroscopy techniques, IR absorption spectroscopy is not intrinsically size-selective. All cluster sizes generated in the expansion are observed together, and indirect methods of size assignment are needed. 

The clusters 59 and 60 (Figure 2.3-12) form an Al cluster framework, which, amongst others, can be described as a distorted section from the structure of solid aluminum, as is shown in addition in Figure 2.3-12 ( molecular nanostructured element modifications ). The alternative description of cluster 59 as a sandwich compound, wherein an Al3+ ion is coordinated by two aromatic AI3R32 rings (cf. Ga3R32, Section 2.3.2), is not confirmed by quantum chemical calculations [89]. 

Although no En cluster molecules with n > 4 are known in the condensed phase, it has been shown [27] that neutral P6 can be generated in the gas phase by neutralization-reionization mass spectrometry with cp 2 6 as a precursor [cp = C5(CH3)5] [28]. Since the cp 2P6 precursor molecule already has a hetero-benzvalene P6 skeleton, it was inferred that the neutral P6 molecule should have the benzvalene structure as shown in Figure 2.6-5. This is in agreement with a multitude of quantum chemical calculations [8, 11, 27, 29-32]. Note that the handle of the basket of P6 includes two dicoordinate P atoms linked by a P=P double bond (cf. R-P=P-R 203 pm [33]). 

Despite many synthetic efforts no P- or As-cluster cations have been characterized in condensed phases to date, although their existence in the gas phase is well established by mass spectrometry and photoionization in combination with quantum chemical calculations (see below). Only one antimony cation is claimed in con-... 

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