Energy transfer of highly vibrationally excited phenanthrene and diphenylacetylene

The energy transfer between Kr atoms and highly vibrationally excited, rotationally cold phenanthrene and diphenylacetylene in the triplet state was investigated using crossed-beam/time-of-flight mass spectrometer/time-sliced velocity map ion imaging techniques. Compared to the energy transfer between naphthalene and Kr, energy transfer between phenanthrene and Kr shows a larger cross-section for vibrational to translational (V → T) energy transfer, a smaller cross-section for translational to vibrational and rotational (T → VR) energy transfer, and more energy transferred from vibration to translation. These differences are further enlarged in the comparison between naphthalene and diphenylacetylene. In addition, less complex formation and significant increases in the large V → T energy transfer probabilities, termed supercollisions in diphenylacetylene and Kr collisions were observed. The differences in the energy transfer between these highly vibrationally excited molecules are attributed to the low-frequency vibrational modes, especially those vibrations with rotation-like wide-angle motions.     

Excitation energy transfer between closely spaced multichromophoric systems: effects of band mixing and intraband relaxation

We theoretically analyze the excitation energy transfer between two closely spaced linear molecular J-aggregates, whose excited states are Frenkel excitons. The aggregate with the higher (lower) exciton band edge energy is considered as the donor (acceptor). The celebrated theory of F?rster resonance energy transfer (FRET), which relates the transfer rate to the overlap integral of optical spectra, fails in this situation. We point out that, in addition to the well-known fact that the point-dipole approximation breaks down (enabling energy transfer between optically forbidden states), also the perturbative treatment of the electronic interactions between donor and acceptor system, which underlies the F?rster approach, in general loses its validity due to overlap of the exciton bands. We therefore propose a nonperturbative method, in which donor and acceptor bands are mixed and the energy transfer is described in terms of a phonon-assisted energy relaxation process between the two new (renormalized) bands. The validity of the conventional perturbative approach is investigated by comparing to the nonperturbative one; in general, this validity improves for lower temperature and larger distances (weaker interactions) between the aggregates. We also demonstrate that the interference between intraband relaxation and energy transfer renders the proper definition of the transfer rate and its evaluation from experiment a complicated issue that involves the initial excitation condition. Our results suggest that the best way of determining this transfer rate between two J-aggregates is to measure the fluorescence kinetics of the acceptor J-band after resonant excitation of the donor J-band.     

Intra- and intermolecular energy transfer in highly excited ozone complexes

The energy transfer of highly excited ozone molecules is investigated by means of classical trajectories. Both intramolecular energy redistribution and the intermolecular energy transfer in collisions with argon atoms are considered. The sign and magnitude of the intramolecular energy flow between the vibrational and the rotational degrees of freedom crucially depend on the projection K(a) of the total angular momentum of ozone on the body-fixed a axis. The intermolecular energy transfer in single collisions between O(3) and Ar is dominated by transfer of the rotational energy. In accordance with previous theoretical predictions, the direct vibrational de-excitation is exceedingly small. Vibration-rotation relaxation in multiple Ar+O(3) collisions is also studied. It is found that the relaxation proceeds in two clearly distinguishable steps: (1) During the time between collisions, the vibrational degrees of freedom are "cooled" by transfer of energy to rotation; even at low pressure equilibration of the internal energy is slow compared to the time between collisions. (2) In collisions, mainly the rotational modes are "cool" by energy transfer to argon.     

n-GaAs(100)、Si(111)表面修饰卟啉分子的光致界面电荷转移特性的研究

利用表面光电压谱研究了四碘化四-(4-三甲胺苯基)卟啉(TTMAPPIH₂)修饰n-GaAS(100)和n-Si(111)半导体表面的光致界面电荷转移特性,结果表明,n-GaAs(100)表面修饰TTMAPPIH₂分子的光致界面电荷转移效率远比n-Si(111)表面修饰的高,并且发现在该卟啉分子的非吸收区也有明显的光致界面电荷转移现象,而与n-Si(111)间则没有这种转移特性。用电化学测量和UV光谱确定了TTMAPPIH₂相对于n-GaAs(100)、n-si(111)的能级位置关系,对TTMAPPIH₂分子与n-GaAs(100)和n-Si(111)间的不同光致界面电荷转移特性进行了解释。     

New Phenomena in Organometallic‐Mediated Radical Polymerization (OMRP) and Perspectives for Control of Less Active Monomers

The impact of reversible bond formation between a growing radical chain and a metal complex (organometallic‐mediated radical polymerization (OMRP) equilibrium) to generate an organometallic intermediate/dormant species is analyzed with emphasis on the interplay between this and other one‐electron processes involving the metal complex, which include halogen transfer in atom transfer radical polymerization (ATRP), hydrogen‐atom transfer in catalytic chain transfer (CCT), and catalytic radical termination (CRT). The challenges facing the controlled polymerization of “less active monomers” (LAMs) are outlined and, after reviewing the recent achievements of OMRP in this area, the perspectives of this technique are analyzed.     

Photoinduced Electron and Energy Transfer in Dyads of Porphyrin Dimer and Perylene Tetracarboxylic Diimide

Two compounds containing a porphyrin dimer and a perylene tetracarboxylic diimide (PDI) linked by phenyl ( 1 ) or ethylene groups ( 2 ) are prepared. The photophysical properties of these two compounds are investigated by steady state electronic absorption and fluorescence spectra and lifetime measurements. The ground state absorption spectra reveal intense interactions between the porphyrin units within the porphyrin dimer, but no interactions between the porphyirn dimer and PDI. The fluorescence spectra suggest efficient energy transfer from PDI to porphyrin accompanied by less efficient electron transfer from porphyrin to PDI. The energy transfer is not affected by the dimeric structure of porphyrin or the linkage between the porphyrin dimer and PDI. However, the electron transfer from porphyrin to PDI is significantly affected by either the linkage between the donor and the acceptor or the polarity of the solvents. The dimeric structure of the porphyrin units in these compounds significantly promotes electron transfer in nonpolar, but not in polar solvents.     

Energy transfer of highly vibrationally excited 2-methylnaphthalene: Methylation effects

The methylation effects in the energy transfer between Kr atoms and highly vibrationally excited 2-methylnaphthalene in the triplet state were investigated using crossed-beam/time-sliced velocity-map ion imaging at a translational collision energy of approximately 520 cm(-1). Comparison of the energy transfer between naphthalene and 2-methylnaphthalene shows that the difference in total collisional cross section and the difference in energy transfer probability density functions are small. The ratio of the total cross sections is sigma(naphthalene): sigma(methylnaphthalene)=1.08+/-0.05:1. The energy transfer probability density function shows that naphthalene has a little larger probability at small T-->VR energy transfer, DeltaE(u)<300 cm(-1), and 2-methylnaphthalene has a little larger probability at large V-->T energy transfer, -800 cm(-1)相似文献   

Ultrafast energy transfer of one-dimensional excitons between carbon nanotubes: a femtosecond time-resolved luminescence study

Excitation energy transfer has long been an intriguing subject in the fields of photoscience and materials science. Along with the recent progress of photovoltaics, photocatalysis, and photosensors using nanoscale materials, excitation energy transfer between a donor and an acceptor at a short distance (≤1-10 nm) is of growing importance in both fundamental research and technological applications. This Perspective highlights our recent studies on exciton energy transfer between carbon nanotubes with interwall (surface-to-surface) distances of less than ～1 nm, which are equivalent to or shorter than the size of one-dimensional excitons in carbon nanotubes. We show exciton energy transfer in bundles of single-walled carbon nanotubes with the interwall distances of ～0.34 and 0.9 nm (center-to-center distances ～1.3-1.4 and 1.9 nm). For the interwall distance of ～0.34 nm (center-to-center distance ～1.3-1.4 nm), the transfer rate per tube from a semiconducting tube to adjacent semiconducting tubes is (1.8-1.9) × 10(12) s(-1), and that to adjacent metallic tubes is 1.1 × 10(12) s(-1). For the interwall distance of ～0.9 nm (center-to-center distance ～1.9 nm), the transfer rate per tube from a semiconducting tube to adjacent semiconducting tubes is 2.7 × 10(11) s(-1). These transfer rates are much lower than those predicted by the F?rster model calculation based on a point dipole approximation, indicating the failure of the conventional F?rster model calculations. In double-walled carbon nanotubes, which are equivalent to ideal nanoscale coaxial cylinders, we show exciton energy transfer from the inner to the outer tubes. The transfer rate between the inner and the outer tubes with an interwall distance of ～0.38 nm is 6.6 × 10(12) s(-1). Our findings provide an insight into the energy transfer mechanisms of one-dimensional excitons.     

Studies on the reaction pathway of arsenate adsorption at water-TiO2 interfaces using density functional theory

A perylenetetracarboxylic diimide (PDI) compound with an attached hydrophilic polyoxyethylene group at the imide nitrogen position was designed and synthesized. Photoinduced electron and energy transfer between coumarin 153 (C-153) and PDI in a ternary microemulsion with an ionic liquid (bmimPF(6)/TX-100/H(2)O) were investigated by steady state electronic absorption and fluorescence spectroscopy. The results revealed that both PDI and C-153 resided at the interface between the surfactant TX-100 and the ionic liquid bmimPF(6) in the ternary microemulsions. The absorption spectra suggested no interactions between C-153 and PDI in the ground states, but the fluorescence spectra revealed the presence of an efficient electron transfer and a less efficient energy transfer from C-153 to PDI. Moreover, the electron transfer was much more efficient in microemulsions than that in homogeneous conventional organic solvents due to the unique micro-environment of the microemulsion.     

Theoretical Study of Structure,Energetic, Hydrogen Bonds Strength and Intramolecular Proton Transfer of 2‐(2‐R (ROH,NH2, SH) Phenyl (or Pyridyl)) Benzoxazoles (or Benzothiazoles)

The ground‐ and excited‐state intramolecular proton transfer processes of 2‐(2‐R (R?OH, NH₂, SH) phenyl (or pyridyl)) benzoxazoles (or benzothiazoles) are investigated by the DFT methods. The calculated results indicate that in the ground state there is a high correlation (R=0.9950) between the proton transfer barrier and the intramolecular hydrogen bonds (IMHB) strength. The increase of the strength of IMHB in the proton transfer processes leads to a larger barrier contributions. Intramolecular proton transfer process pathway is along with the minimal difference of change value in the IMHB angle. In the excited‐state, there is a similar relationship between the IMHB and the barrier.     

Insight into the phosphoryl transfer of the Escherichia coli glucose phosphotransferase system from QM/MM simulations

Phosphoryl transfer is a key reaction in many aspects of metabolism, gene regulation, and signal transduction. One prominent example is the phosphoenolpyruvate:sugar phosphotransferase system (PTS), which represents an integral part of the bacterial sugar metabolism. The transfer between the enzymes IIA (Glc) and IIB (Glc) in the glucose-specific branch of the PTS is of particular interest due to the unusual combination of donor and acceptor residues involved in phosphoryl transfer: The phosphoryl group is initially attached to the Nepsilon2 atom of His 90 in IIA (Glc) and then transferred to the S gamma atom of Cys 35 in IIB (Glc). To gain insight into the details of the transfer mechanism, we have performed a QM/MM simulation which treats the entire active site quantum-mechanically. The transfer has a high dissociative character, and the Nepsilon2-P bond gets immediately destabilized after complex formation by numerous interactions formed between residues of IIB (Glc) and the phosphoryl group. The final formation of a tight S gamma-P bond is accompanied by a reorientation of the side chain of the phosphoryl donor. This reorientation results in the loss of interaction between the imidazole ring and the phosphate group thus hindering the reverse transfer. A comparison to the transfer in protein tyrosine phosphatases, which also use a cysteine as acceptor of the phosphoryl group, reveals significant similarities in the conformation of the active site, the energy profile of the reaction, and in the pattern of interactions that stabilize the phosphoryl group during the transfer.     

Energy transfer of highly vibrationally excited naphthalene: collisions with CHF3, CF4, and Kr

Energy transfer of highly vibrationally excited naphthalene in the triplet state in collisions with CHF(3), CF(4), and Kr was studied using a crossed-beam apparatus along with time-sliced velocity map ion imaging techniques. Highly vibrationally excited naphthalene (2.0 eV vibrational energy) was formed via the rapid intersystem crossing of naphthalene initially excited to the S(2) state by 266 nm photons. The shapes of the collisional energy-transfer probability density functions were measured directly from the scattering results of highly vibrationally excited naphthalene. In comparison to Kr atoms, the energy transfer in collisions between CHF(3) and naphthalene shows more forward scatterings, larger cross section for vibrational to translational (V → T) energy transfer, smaller cross section for translational to vibrational and rotational (T → VR) energy transfer, and more energy transferred from vibration to translation, especially in the range -ΔE(d) = -100 to -800 cm(-1). On the other hand, the difference of energy transfer properties between collisional partners Kr and CF(4) is small. The enhancement of the V → T energy transfer in collisions with CHF(3) is attributed to the large attractive interaction between naphthalene and CHF(3) (1-3 kcal/mol).     

A mechanistic dichotomy in scandium ion-promoted hydride transfer of an NADH analogue: delicate balance between one-step hydride-transfer and electron-transfer pathways

The rate constant (kH) of hydride transfer from an NADH analogue, 9,10-dihydro-10-methylacridine (AcrH2), to 1-(p-tolylsulfinyl)-2,5-benzoquinone (TolSQ) increases with increasing Sc(3+) concentration ([Sc(3+)]) to reach a constant value, when all TolSQ molecules form the TolSQ-Sc(3+) complex. When AcrH2 is replaced by the dideuterated compound (AcrD2), however, the rate constant (kD) increases linearly with an increase in ([Sc(3+)]) without exhibiting a saturation behavior. In such a case, the primary kinetic deuterium isotope effect (kH/kD) decreases with increasing ([Sc(3+)]). On the other hand, the rate constant of Sc(3+)-promoted electron transfer from tris(2-phenylpyridine)iridium [Ir(ppy)3]to TolSQ also increases linearly with increasing ([Sc(3+)]) at high concentrations of Sc(3+) due to formation of a 1:2 complex between TolSQ*- and Sc(3+), [TolSQ*--(Sc(3+)2], which was detected by ESR. The significant difference with regard to dependence of the rate constant of hydride transfer on ([Sc(3+)]) between AcrH2 and AcrD2 in comparison with that of Sc3+-promoted electron transfer indicates that the reaction pathway is changed from one-step hydride transfer from AcrH2 to the TolSQ-Sc3+ complex to Sc3+-promoted electron transfer from AcrD2 to the TolSQ-Sc3+ complex, followed by proton and electron transfer. Such a change between two reaction pathways, which are employed simultaneously, is also observed by simple changes of temperature and concentration of Sc3+.     

别嘌醇质子迁移过程的理论研究

别嘌醇(Allopurinol)是次黄嘌呤的位置异构体,是唯一在临床上应用的黄嘌呤氧化酶抑制剂.     

有机铼化合物互变异构反应机理的理论研究

采用B3LYP方法研究了有机铼化合物(Me)2(NHR3)Re(=CHR1)(=NR2)与(Me)2(NHR3)Re(≡CR1)(NHR2)之间的异构化反应机理(R1, R2, R3=H, Me, But). 确定了相应的过渡态结构和反应活化能.结果表明, 分子内氢转移过程所需活化能很大;两个反应物分子间的氢转移过程需要的活化能也较大;分子与水间氢转移需要的活化能较小, 分子与HCl间氢转移需要的活化能最小. 结果还表明, 对所研究的四种途径, 取代基对反应活化能的影响相同, R1=Me或But, R2=H, R3=But时反应活化能最小, 并且取代基对反应活化能的影响存在加和性.     

Photoinduced electron transfer in naphthalimide-pyridine systems: effect of proton transfer on charge recombination efficiencies

We studied the effect of proton-coupled electron transfer on lifetimes of the charge-separated radicals produced upon light irradiation of the thiomethyl-naphthalimide donor SMe-NI-H in the presence of nitro-cyano-pyridine acceptor (NO(2)-CN-PYR). The dynamics of electron and proton transfer were studied using femtosecond pump-probe spectroscopy in the UV/vis range. We find that the photoinduced electron transfer between excited SMe-NI-H and NO(2)-CN-PYR occurs with a rate of 1.1 × 10(9) s(-1) to produce radical ions SMe-NI-H(?+) and NO(2)-CN-PYR(?-). These initially produced radical ions in a solvent cage do not undergo a proton transfer, possibly due to unfavorable geometry between N-H proton of the naphthalimide and aromatic N-atom of the pyridine. Some of the radical ions in the solvent cage recombine with a rate of 2.3 × 10(10) s(-1), while some escape the solvent cage and recombine at a lower rate (k = 4.27 × 10(8) s(-1)). The radical ions that escape the solvent cage undergo proton transfer to produce neutral radicals SMe-NI(?) and NO(2)-CN-PYR-H(?). Because neutral radicals are not attracted to each other by electrostatic interactions, their recombination is slower that the recombination of the radical ions formed in model compounds that can undergo only electron transfer (SMe-NI-Me and NO(2)-CN-PYR, k = 1.2 × 10(9) s(-1)). The results of our study demonstrate that proton-coupled electron transfer can be used as an efficient method to achieve long-lived charge separation in light-driven processes.     

Interferometric coherence transfer modulations in triply vibrationally enhanced four-wave mixing

Triply vibrationally enhanced (TRIVE) four-wave mixing (FWM) spectroscopy in a mixed frequency/time domain experiment contains new output coherences that isolate nonlinear pathways that involve coherence transfer. Coherence transfer occurs when a thermal bath induces coupling between two states so a quantum mechanical entanglement of a pair of quantum states evolves to entangle a new pair of quantum states. The FWM includes several equivalent coherence pathways that interfere and create a temporal modulation of the output coherence that is a signature of coherence transfer. The transfer shifts the output coherence frequency and isolates coherence transfer pathways from the stronger FWM processes that form the basis of coherent multidimensional spectroscopy. The use of coherence transfer offers the opportunity for another form of coherent multidimensional spectroscopy where cross-peaks appear because of the coherence transfer between quantum states. Since this approach is based on frequency domain methods, it requires only short-term phase coherence during the excitation process so the method is not constrained to accessing the quantum states lying within the excitation pulse bandwidth.     

Slow hydrogen atom self-exchange between Os(IV) anilide and Os(III) aniline complexes: relationships with electron and proton transfer self-exchange

Hydrogen atom, proton and electron transfer self-exchange and cross-reaction rates have been determined for reactions of Os(IV) and Os(III) aniline and anilide complexes. Addition of an H-atom to the Os(IV) anilide TpOs(NHPh)Cl(2) (Os(IV)NHPh) gives the Os(III) aniline complex TpOs(NH(2)Ph)Cl(2) (Os(III)NH(2)Ph) with a new 66 kcal mol(-1) N-H bond. Concerted transfer of H* between Os(IV)NHPh and Os(III)NH(2)Ph is remarkably slow in MeCN-d(3), with k(ex)(H*) = (3 +/- 2) x 10(-3) M(-1) s(-1) at 298 K. This hydrogen atom transfer (HAT) reaction could also be termed proton-coupled electron transfer (PCET). Related to this HAT process are two proton transfer (PT) and two electron transfer (ET) self-exchange reactions, for instance, the ET reactions Os(IV)NHPh + Os(III)NHPh(-) and Os(IV)NH(2)Ph(+) + Os(III)NH(2)Ph. All four of these PT and ET reactions are much faster (k = 10(3)-10(5) M(-1) s(-1)) than HAT self-exchange. This is the first system where all five relevant self-exchange rates related to an HAT or PCET reaction have been measured. The slowness of concerted transfer of H* between Os(IV)NHPh and Os(III)NH(2)Ph is suggested to result not from a large intrinsic barrier but rather from a large work term for formation of the precursor complex to H* transfer and/or from significantly nonadiabatic reaction dynamics. The energetics for precursor complex formation is related to the strength of the hydrogen bond between reactants. To probe this effect further, HAT cross-reactions have been performed with sterically hindered aniline/anilide complexes and nitroxyl radical species. Positioning steric bulk near the active site retards both H* and H(+) transfer. Net H* transfer is catalyzed by trace acids and bases in both self-exchange and cross reactions, by stepwise mechanisms utilizing the fast ET and PT reactions.     

Sub-Tc electron transfer at the HTSC/polymer interface

The first kinetic measurements for electron transfer (ferrocene/ferricinium reaction) at the interface between an HTSC (Tl,Pb1223) and a redox polymer (ferrocene-tagged poly-pyrrole) show that superconductivity affects electron transfer rate, which thus offers a novel probe of the superconducting state.     

Electron delocalization in mixed-valence Keggin polyoxometalates. Ab initio calculation of the local effective transfer integrals and its consequences on the spin coupling

We present a quantitative evaluation of the influence of the electron transfer on the magnetic properties of mixed-valence polyoxometalates reduced by two electrons. For that purpose, we extract from valence-spectroscopy ab initio calculations on embedded fragments the value of the transfer integrals between W nearest-neighbor atoms in a mixed-valence alphaPW(12)O(40) polyoxowolframate Keggin anion. In contradiction with what is usually assumed, we show that the electron transfer between edge-sharing and corner-sharing WO(6) octahedra have very close values. Considering fragments of various ranges, we analyze the accuracy of calculations on fragments based on only two WO(5) pyramids which should allow a low cost general study of transfer parameters in polyoxometalates. Finally, these parameters are introduced in an extended Hubbard Hamiltonian that models the whole anion. It permits to prove that electron transfers induce a large energy gap between the singlet ground state and the lowest triplet states providing a clear explanation of the diamagnetic properties of the mixed-valence Keggin ions reduced by two electrons.