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61.
We present a theoretical study of dissociative photoionization of H2 via the 1Πu symmetry in the photon energy range 30–43 eV. Our results explain the various peaks observed in the experiments below 40 eV and illustrate, in particular, the important role of the 2Πu(2pπu) ionization threshold. At higher photon energies, they suggest the existence of new resonance structures that may be associated with doubly excited states of H2 lying above the third and fourth ionization thresholds (the Q3 and Q4 resonance series). From the calculated resonance parameters, we conclude that the dominant mechanism at high photon energies should involve the Q4 (and probably higher) doubly excited states of H2. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2002 相似文献
62.
Dr. Alexey S. Kiryutin Mikhail S. Panov Dr. Alexandra V. Yurkovskaya Prof. Dr. Konstantin L. Ivanov Prof. Dr. Geoffrey Bodenhausen 《Chemphyschem》2019,20(5):766-772
A study of long-lived spin order in chlorothiophene carboxylates at both high and low magnetic fields is presented. Careful sample preparation (removal of dissolved oxygen in solution, chelating of paramagnetic impurities, reduction of convection) allows one to obtain very long-lived singlet order of the two coupled protons in chlorothiophene derivatives, having lifetimes of about 130 s in D2O and 240 s in deuterated methanol, which are much longer than the T1-relaxation times (18 and 30 s, respectively, at a field =9.4 T). In protonated solvents the relaxation times become shorter, but the lifetime is still substantially longer than . In addition, long-lived coherences are shown to have lifetimes as long as 30 s. Thiophene derivatives can be used as molecular tags to study slow transport, slow dynamics and slow chemical processes, as has been shown in recent years. 相似文献
63.
YUAN Liwei WANG Yanqiu WANG Li BAI Jiling & HE Guozhong State Key Laboratory of Molecular Reaction Dynamics Dalian Institute of Chemical Physics Chinese Academy of Sciences Dalian China 《中国科学B辑(英文版)》2004,47(4)
Dichlorobenzene is a precursor molecule of di-oxins, which are some of the most toxic chemicals and are suspected of being mutagenic with the structure of benzene rings containing different numbers of chlorine atoms. They are seriously harmful to the health of human. Therefore, it is necessary to study these aryl chemicals especially dichlorobenzene molecules in great detail. In recent years, a number of groups have investi-gated the molecules of aryl halide. The near ultraviolet absorption sp… 相似文献
64.
Summary Time-dependent perturbation theory has been applied to calculate the doubly excited triplet statesNsns:3Se,Npnp:3De andNdnd:3Ge (N=2, 3, 4,n=N+1, ... ,5) for He, Li+, Be2+ and B3+. A time-dependent harmonic perturbation causes simulataneous excitation of both the electrons with a change of spin state. The doubly excited energy levels have been identified as the poles of an appropriately constructed linearized variational functional with respect to the driving frequency. In addition to the transition energies, effective quantum numbers of these doubly excited states have been calculated and analytic representations of their wave functions are obtained. These are utilized to estimate the Coulomb repulsion term for these states which checks the consistency of the wave functions. These wave functions may also be used for calculating other physical properties of the systems. 相似文献
65.
近年来,实验发现钛酸铅基材料具有负热膨胀性,且其热膨胀程度会受到掺杂元素的影响. 目前所研究的A位掺杂体系中,仅Cd原子掺杂能使钛酸铅负热膨胀性增强. 所以研究A位掺杂钛酸铅,比较Cd原子与其他原子在掺杂钛酸铅时化学键的异同,有助于深刻理解钛酸铅负热膨胀的本质. 本文利用第一性原理,分别优化了Sr、Ba、Cd掺杂钛酸铅的晶格常数,计算了它们的态密度和电荷密度. 结果表明Cd―O键的共价性强于Pb―O键,而Ba―O键和Sr―O键几乎呈离子性,Ba/Sr对Pb的替代削弱了化合物的共价性,降低了自发极化强度. 与实验测量的热膨胀系数对比可以发现,A位原子与氧原子之间的共价性增强,化合物负热膨胀程度升高;若A位原子与氧原子之间的共价性削弱,负热膨胀程度降低. 可见A位原子与氧原子之间的共价性影响了钛酸铅基化合物负热膨胀性. 相似文献
66.
We calculate energy barriers of atom- and proton-transfer reactions in hydrogen-bonded complexes in the gas phase. Our calculations do not involve adjustable parameters and are based on bond-dissociation energies, ionization potentials, electron affinities, bond lengths, and vibration frequencies of the reactive bonds. The calculated barriers are in agreement with experimental data and high-level ab initio calculations. We relate the height of the barrier with the molecular properties of the reactants and complexes. The structure of complexes with strong hydrogen bonds approaches that of the transition state, and substantially reduces the barrier height. We calculate the hydrogen-abstraction rates in H-bonded systems using the transition-state theory with the semiclassical correction for tunneling, and show that they are in excellent agreement with the experimental data. H-bonding leads to an increase in tunneling corrections at room temperature. 相似文献
67.
The possibility of excited‐state protomeric shifts in the biologically important molecule, alloxan, is investigated. We have focused on the S1 and T1 excited states of alloxan and its hydroxy tautomers. Modifications brought in by excitation on the relative stabilities, activation barriers, and optimized geometries, computed at the MNDO, AM1, and PM3 levels of approximation, have been discussed for both excited electronic states. The absorption and fluorescence spectra for the three tautomers are also discussed. Results show significant changes in the geometries on excitation, although the changes are similar for the singlet and triplet excited states. Though the relative stability orders do not change, the 2‐hydroxy tautomer is stabilized, while the 4‐hydroxy tautomer gets destabilized on excitation. The excited states are (n,π*) states, involving the promotion of a nonbonding oxygen lone pair from the CO? CO? CO moiety, which explains why the oxygens of this group become less basic and the 4‐hydroxy tautomer gets destabilized on excitation. However, the activation barriers do not reduce significantly on excitation, and this precludes the possibility of ground‐ or excited‐state proton transfer in the gas phase. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2001 相似文献
68.
Filip Fratev Gottfried Olbrich Oskar E. Polansky 《Monatshefte für Chemie / Chemical Monthly》1979,110(3):505-515
UsingGleason's theorem the pars orbital concept is developed for excited states of conjugated systems described by CI-methods. A significance index is introduced to evaluate different patterns of fragmentation. The usefulness of this approach is illustrated for butadiene, biphenyl, naphthalene, and azulene.
11. Mitt.:H. Karpf, O. E. Polansky undM. Zander, Tetrahedron Lett.1978, 2069. 相似文献
69.
70.
Energized molecules are the essential actors in chemical transformations in solution. As the rearrangement of bonds requires a movement of nuclei, vibrational energy is often the driving force for a reaction. Vibrational energy can be redistributed within the "hot" molecule, or relaxation can occur when molecules interact. Both processes govern the rates, pathways, and quantum yields of chemical transformations in solution. Unfortunately, energy transfer and the breaking, formation, and rearrangement of bonds take place on ultrafast timescales. This Review highlights experimental approaches for the direct, ultrafast measurement of photoinduced femtochemistry and energy flow in solution. In the first part of this Review, we summarize recent experiments on intra- and intermolecular energy transfer. The second part discusses photoinduced decomposition of large organic peroxides, which are used as initiators in free radical polymerization. The mechanisms and timescales of their decarboxylation determine the initial steps of polymerization and the microstructure of the polymer product. 相似文献