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51.
Hidemasa Azuma Yuzuru Katagiri Shinichi Yamabe 《Journal of polymer science. Part A, Polymer chemistry》1996,34(8):1407-1414
Transition states (TSs) of radical addition homopolymerization reactions of methyl acrylate, methyl methacrylate, dimethyl itaconate, and N-methyl itaconimide were examined with two-unit radical models using MOPAC (PM3 UHF) semiempirical method. Calculated activation energies (Eas) show good correlations with experimental values. Calculated activation entropies (−ΔS‡s) are found to be well proportional to Eas. The entropy terms play an important role as well as Ea in radical additions. Ea depends on the angle (θrs) between reaction points of radical and of monomer at TS. The bond length between reaction points at TS is constant regardless of monomers studied. The geometries and thermodynamical properties calculated here for TS indicate the importance of steric effects caused by substituted group(s) rather than electronic perturbation energies reported previously. © 1996 John Wiley & Sons, Inc. 相似文献
52.
Guigang Zhang Xinchen Wang 《Angewandte Chemie (International ed. in English)》2019,58(44):15580-15582
Photocatalytic overall water splitting by sulfide‐based materials is a great challenge because of the poor resilience of such materials against hole oxidation. In a recent study, Domen and co‐workers developed an innovative strategy to stabilize sulfide‐based photocatalysts by hybridizing S 3p with O 2p orbitals to produce oxysulfides in which S2? is stable. Further surface engineering of the oxysulfides with dual co‐catalysts promoted charge separation and interface transfer, thus reducing the charge build‐up that inhibits photocorrosion. The pH value of the reaction mixture is a critical consideration for achieving efficient stoichiometric H2 and O2 evolution by these oxysulfide photocatalysts. 相似文献
53.
Recyclable MoO3 nanobelts for photocatalytic degradation of Rhodamine B by near infrared irradiation
Molybdenum trioxide (MoO3) represented an excellent photocatalytic performance with many applications, including degradation of organic contaminants and splitting of water. This paper presented a new route to synthesize MoO3 nanobelts with high aspect ratios and crystallinity by a hydrothermal technique. This work showed that the as-synthesized nanobelts exhibited strong photocatalytic activity to degrade an organic dye of Rhodamine B (RhB) in aqueous solution under the exposure of the light source in the near infrared wavelength range, significantly improving the photocatalytic activity of the nanobelts. The results also showed that for a small concentration of RhB at 7.5 mg/L a complete photodegradation (for a given MoO3 nanobelts quantity of 0.1 g) can be reached after exposing for 60 min. For all concentrations of the RhB solution, the photodegradation exhibited an exponential dependence on the exposure time followed by a sudden shutdown, but no complete photodegradation can be reached. Also, the residual quantity of RhB in solution after the photocatalytic reaction was determined by the initial RhB concentration. The photocatalytic degradation can be interpreted by the pseudo–first-order equation for the absorption of liquid/solid based on solid capacity; thus, photocatalytic degradation can be attributed to the interaction between the photoexcited electrons in the substrate and the antibonding orbital of the RhB in solution. The sudden shutdown was due to the inability of the photoexcited electrons in the substrate hopping to the antibonding orbital of RhB in the presence of the RhB intermediate products from the degraded RhB. In addition, this work showed that the photocatalytic reaction can be recovered after a thermal treatment of postreacted MoO3 nanobelts, enhancing the utilization efficiency of the catalysis. 相似文献
54.
Ab initio molecular orbital calculations for N9, N−
9 and N+
9 isomers were carried out at the HF/ 6-31G*, B3PW91/6-31G*, B3LYP/6-31G* and MP2/ 6-31G* levels of theory. Stable equilibrium
geometric structures were determined by harmonic vibrational frequency analyses at the HF/6-31G*, B3PW91/6-31G* and B3LYP/6-31G*
levels of theory. The most stable free-radical N9 cluster is structure 1 with C
2
v
symmetry and that of anion N−
9 is structure 3 with C
s
symmetry. Only one stable structure of the N+
9 cation with C
2
v
symmetry was predicted. Their potential application as high-energy-density materials has been examined.
Received: 15 June 1999 / Accepted: 11 October 1999 / Published online: 14 March 2000 相似文献
55.
The orbital deletion procedure is introduced, which is suited to quantitatively investigating the electronic delocalization effiect in earboeations and boranes. While the routine, ab initio molecular orbital methods can generate wavefunetions for real systems where all electrons are delocalized, the present orbital deletion procedure can generate wavefunctions for hypothetical reference molecules where electronic delocalization effect is deactivated. The latter wavefunetion normlly corresponds In the most stable resonance structure in terms of the resonance theory. By comparing and analyzing the delocalized and the localized wavefunetions, one can obtain a quantitative and instinct pieture to show how electronic deloealizalion inside a molecule affects the molecular structure, energy as well as other physical properties. Two examples are detailedly discussed. The first is related to the hypercoujugation of alkyl groups in carbocations and a comparison of the order of stability of carbocations is made, T 相似文献
56.
E. G. Gal'pern I. V. Stankevich A. L. Chistyakov L. A. Chernozatonskii 《Russian Chemical Bulletin》1999,48(11):2039-2045
Molecular and electronic structure of four polyhydrogenated (n,0)-tubulenes, namely, [−C24H4−]
m
(1), two isomers of composition [−C28H4−]
m
(2 and3), and [−C32H4−]
m
(4) withn benzene rings in the cross section (n=6, 7, 7, and 8, respectively), was simulated atm>1 (m is the number of repeating fragemnts). It was assumed that hydrogen atoms are attached to all carbon atoms lying on the two
most distant elements of the cylinders of the corresponding tubulenes. The energy band structures of macromolecules1–4 and their Li-intercalated analogs [−C24H4Li−]
m
(5) [−C28H4Li−]
m
(two isomers,6 and7), and [−C32H4Li−]
m
(8), containing one Li atom per repeating unit at each center, were obtained in the EHT approximation by the crystal orbital
method. Geometric parameters of repeating units of structures1–8 were found after MNDO/PM3 optimization of the energies of hydrocarbon molecules C72H24, C84H26 (two geometric isomers), and C96H28, containing three repeating units of corresponding tubulenes1–4 each. The conductivity types of polyhydrogenated tubulenes1–4 are the same as those of their precursors, (6,0)-, (7,0)-, and (8,0)-tubulenes. Dispersion curves of systems5–8 are much the same as those of macromolecules1–4; however, electron energy spectra of5–8 possess metallic conductivity type and the positions of Fermi levels for these systems are higher than for compounds1–4.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2061–2067, November, 1999. 相似文献
57.
Ariafard A Brookes NJ Stranger R Yates BF 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(20):6119-6124
Molecular orbital theory has been used to study a series of [(micro-N2){ML3}2] complexes as models for dinitrogen activation, with M=Mo, Ta, W, Re and L=NH2, PH2, AsH2, SbH2 and N(BH2)2. The main aims of this study have been to provide a thorough electronic analysis of the complexes and to extend previous work involving molecular orbital analyses. Molecular orbital diagrams have been used to rationalize why for L=NH2 ligand rotation is important for the singlet state but not the triplet, to confirm the effect of ligand pi donation, and to rationalize the importance of the metal d-electron configuration. The outcomes of this study will assist with a more in-depth understanding of the electronic basis for N2 activation and allow clearer predictions to be made about the structure and multiplicity of systems involved in transition-metal catalysis. 相似文献
58.
I. I. Guseinov 《Journal of mathematical chemistry》2009,45(4):1166-1169
S. ?zcan and E. ?ztekin, (J. Math. Chem. doi:) published formulas for evaluating the two-center nuclear attraction integrals over Slater type orbitals. It is shown that
the analytical relations for these integrals through the expansion coefficients of the electron charge density for the one-center
case and the overlap integrals presented in Sect. 3 of this work can easily be derived by means of a simple algebra from the
formulas published in our papers (I.I. Guseinov, J Mol Struct (Theochem) 417:117, 1997; J Math Chem 42:415, 2007 and B.A.
Mamedov, Chin J Chem 22:545, 2004). It should be noted that the formulas of overlap integrals presented by E. ?ztekin et al.,
in previous paper (E. ?ztekin, M. Yavuz, Ş. Atalay, J Mol Struct (Theochem) 544:69, 2001) for the calculation of two-center
nuclear attraction integrals also are obtained from our papers (see Comment: I.I. Guseinov, J Mol Struct (Theochem) 638:235,
2003). 相似文献
59.
The concept of orbital compatibility is used to explain the relative energies of different macropolyhedral structural patterns such as closo‐closo, closo‐nido, and nido‐nido. A large polyhedral borane condenses preferentially with a smaller polyhedron owing to orbital compatibility. Calculations carried out at the B3LYP/6‐31G* level show that the macropolyhedron closo(12)‐closo(6) is the most preferred structural pattern among the face‐sharing closo‐closo systems. The relative stabilities of four‐shared‐atom closo‐closo, three‐shared‐atom closo‐closo, three‐shared‐atom closo‐nido, edge‐sharing closo‐nido, and edge‐sharing nido‐nido structures are in accordance with the difference in the number of vertices of the individual polyhedra of the macropolyhedra. When the difference in the number of vertices of the individual polyhedra is large, the stability of the macropolyhedra is also large. Calculations further show that the orbital compatibility plays an important role in deciding the stability of the macropolyhedral boranes with more than two polyhedral units. The dependence of the orbital compatibility on the relative stability of the macropolyhedron varies with other factors such as inherent stability of the individual polyhedron and steric factors. 相似文献
60.
Fourteen conformers of 3-amino-1-propanol as the minima on the potential energy surface are examined at the MP2/6-311++G** level. Their relative energies calculated at B3LYP, MP3 and MP4 levels of theory indicated that two most stable conformers display the in-tramolecular OH…N hydrogen bonds. The vertical ionization energies of these conformers calculated with ab initio electron propagator theory in the P3/aug-cc-pVTZ approximation are in agreement with experimental data from photoelectron spectroscopy. Natural bond orbital analyses were used to explain the differences of IEs of the highest occupied molec-ular ortibal of conformers. Combined with statistical mechanics principles, conformational distributions at various temperatures are obtained and the temperature dependence of pho-toelectron spectra is interpreted. 相似文献