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71.
耦合双原子Jaynes-Cummings模型的腔场谱H 总被引:14,自引:8,他引:6
研究了处于激发态的两原子与高Q腔场相互作用单光子过程的腔场谱,给出了初始光场为光子数态、相干态、压缩真空态时的腔场谱数值计算结果,分析了原子间偶极-偶极相互作用强度gα对腔场谱结构的影响.发现真空场Rabi峰,当gα较弱时为4峰,gα较强时为3峰结构;弱场数态(n>0)时为5峰,强场时为3峰结构.相干态和压缩真空态时,谱结构与光子数分布有关,一般为复杂的多峰结构.结果表明,gα对峰位峰高都有影响,破坏了谱结构的对称性,但这种影响只在真空场和弱场时才较明显. 相似文献
72.
73.
A novel class of platinum-based initiating systems for the ring-opening polymerization of a wide variety of heterocyclic compounds including epoxides, oxetanes, and 1,3,5-trioxane have been discovered. In addition to a platinum complex as a catalyst, a cocatalyst, consisting of a compound or polymer containing silicon-hydrogen bonds must also be present. This article reports on a preliminary survey of the scope and limitations of these new initiator systems. Particular emphasis in this article has been placed on the ring-opening polymerization of epoxides which have been studied in some detail and which proceed rapidly and exothermically at room temperature. A number of mechanistic studies have been conducted and the best current evidence suggests that polymerization proceeds by a cationic mechanism. Evidence is also presented which suggests that platinum metal colloids may function as the active initiating species. 相似文献
74.
Dithiocarbamate functions were incorporated into different polyacrylamide matrices crosslinked with a flexible and hydrophilic
crosslinking agent, tetraethyleneglycol diacrylate (TEGDA), and their complexation behaviours were investigated. Crosslinked
polyacrylamides with varying extents of the tetrafunctional TEGDA crosslinks were prepared by free radical solution polymerization
at 60°C using potassium persulphate as initiator in ethanol. The dithiocarbamate functionality was incorporated into these
polyacrylamides by a two-step polymer-analogous reaction involving (i)trans-amidation with ethylenediamine and (ii) dithiocarbamylation of the aminopolyacrylamide with carbon disulphide and alkali.
The complexations of dithiocarbamate with Cu(II), Ni(II), Zn(II), Co(II) and Hg(II) ions were followed under different conditions.
The metal ion intake varied with the extent of the crosslinking agent and the observed trend in complexation is Hg(II) > Cu(II)>
Zn(II)> Co(II)> Ni (II). The time-course of complexation, the possibility of recycling, swelling characteristics, and spectral
and thermal analyses were carried out. The thermal stability increases upon complexation with metal ions. 相似文献
75.
Brad M. Rosen Virgil Percec 《Journal of polymer science. Part A, Polymer chemistry》2007,45(21):4950-4964
Atom transfer radical polymerization (ATRP) and single electron‐transfer living radical polymerization (SET‐LRP) both utilize copper complexes of various oxidation states with N‐ligands to perform their respective activation and deactivation steps. Herein, we utilize DFT (B3YLP) methods to determine the preferred ligand‐binding geometries for Cu/N‐ligand complexes related to ATRP and SET‐LRP. We find that those ligands capable of achieving tetrahedral complexes with CuI and trigonal bipyramidal with axial halide complexes with [CuIIX]+ have higher energies of stabilization. We were able to correlate calculated preferential stabilization of [CuIIX]+ with those ligands that perform best in SET‐LRP. A crude calculation of energy of disproportionation revealed that the same preferential binding of [CuIIX]+ results in increased propensity for disproportionation. Finally, by examining the relative energies of the basic steps of ATRP and SET‐LRP, we were able to rationalize the transition from the ATRP mechanism to the SET‐LRP mechanism as we transition from typical nonpolar ATRP solvents to polar SET‐LRP solvents. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4950–4964, 2007 相似文献
76.
Cynthia Kolb Whitney 《Foundations of Physics》2007,37(4-5):788-812
This paper revisits the historical sequence in which some of the major developments of 20th-century physics occurred, and
explores how theories could have turned out differently, if the sequence of developments had been different. It shows how
a delay in founding special relativity theory until after (1) at least one puzzling problem in electromagnetic theory could
be acknowledged, and (2) sat least some of the experimental observations pertinent to the development of quantum mechanics
had become well known, could have resulted in a larger theory that covers both domains in a manner quite different from that
of any of the theories we use today. The revised theory dispenses with a separate postulate introducing Planck’s constant
h, identifying instead a physical mechanism that implies the constant. Some important aspects of quantum chemistry then follow.
Editor, Galilean Electrodynamics, Proceedings of the Natural Philosophy Alliance; Visiting Industry Professor, Tufts University,
retired 相似文献
77.
The constants of binding dye molecules with the micelles of sodium dodecyl sulfate are determined using quenching of delayed fluorescence of acridine dyes by sodium iodide in aqueous–micellar solutions. Kinetic equations have been composed that describe the processes of deactivation of the excited states of dyes. By solving these equations at the concentration of the quencher sodium iodide corresponding to the minimum lifetime of triplet states and at the concentration of micelles corresponding to the least value of the delayed fluorescence quenching rate constants, we obtained the constants of binding dyes with micelles equal to 1.3·107, 2.9·107, and 3.1·107 M–1 for trypaflavine, acridine orange, and acridine yellow, respectively. We calculated the rate constants of quenching of the triplet states of the molecules of dyes by iodide ions (I
–) that decreased in transition from trypaflavine to acridine orange and acridine yellow. 相似文献
78.
R. B. King 《Russian Chemical Bulletin》1993,42(11):1772-1781
Reactions of disodium tetracarbonylferrate, Na2Fe(CO)4, with sterically hindered dialkylaminodichlorophosphines, R2NPCl2 (R2N=diisopropylamino, dicyclohexylamino, and 2,2, 6, 6-tetramethylpiperidino) in diethyl ether lead to the air-stable phosphorus-bridging carbonyl derivatives (R2NP)2COFe2(CO)6 as the major products. The phosphorus-bridging carbonyl group in (i-Pr2NP)2COFe2(CO)6 has been found to undergo the following types of reactions: 1)Reduction, 2)Acylation, 3)Extrusion of the carbonyl group. The mechanisms of the reactions have been considered.This work was presented at the Workshop «The Modern Problems of Heteroorganic Chemistry» held on the ship «Nikolai Bauman» during the period May 8–13, 1993.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1858–1867, November, 1993. 相似文献
79.
Summary Complete Active-Space Self-Consistent-Field (CAS-SCF) calculations for cubic N8 are presented. We studied the N8↔4N2 reaction inD
4h
symmetry and found its energy release and activation barrier with three different atomic basis sets. The energy release for
this reaction is predicted to be around 526 kcal/mol, while the energy barrier to dissociation is estimated about 159 kcal/mol.
These results are in substantial agreement with previousab initio estimates.
The authors of this paper have agreed to not receive the proofs for correction. 相似文献
80.
本文用数字散斑相关方法测量了五种不同幂硬化指数韧性金属材料(铝和铜),双边裂纹尖端细观区域内应变场.对所得结果用韧性损伤模型进行了分析.在此法中以金属自然表面结构为散斑场,不同加载状态的散斑场进行比较,得到相对变形与应变.图象之间相关性 C 是变形参数或是位移及其导数的泛函.使其相关性 C 取最大值的试凑变形即为其真实变形场.这一方法在细观测量中应用得到满意的结果. 相似文献