共查询到20条相似文献，搜索用时 312 毫秒
1.
Li W Zhou X Lock R Patchkovskii S Stolow A Kapteyn HC Murnane MM 《Science (New York, N.Y.)》2008,322(5905):1207-1211
The attosecond time-scale electron-recollision process that underlies high harmonic generation has uncovered extremely rapid electronic dynamics in atoms and diatomics. We showed that high harmonic generation can reveal coupled electronic and nuclear dynamics in polyatomic molecules. By exciting large amplitude vibrations in dinitrogen tetraoxide, we showed that tunnel ionization accesses the ground state of the ion at the outer turning point of the vibration but populates the first excited state at the inner turning point. This state-switching mechanism is manifested as bursts of high harmonic light that is emitted mostly at the outer turning point. Theoretical calculations attribute the large modulation to suppressed emission from the first excited state of the ion. More broadly, these results show that high harmonic generation and strong-field ionization in polyatomic molecules undergoing bonding or configurational changes involve the participation of multiple molecular orbitals. 相似文献
2.
Wörner HJ Bertrand JB Fabre B Higuet J Ruf H Dubrouil A Patchkovskii S Spanner M Mairesse Y Blanchet V Mével E Constant E Corkum PB Villeneuve DM 《Science (New York, N.Y.)》2011,334(6053):208-212
Conical intersections play a crucial role in the chemistry of most polyatomic molecules, ranging from the simplest bimolecular reactions to the photostability of DNA. The real-time study of the associated electronic dynamics poses a major challenge to the latest techniques of ultrafast measurement. We show that high-harmonic spectroscopy reveals oscillations in the electronic character that occur in nitrogen dioxide when a photoexcited wave packet crosses a conical intersection. At longer delays, we observe the onset of statistical dissociation dynamics. The present results demonstrate that high-harmonic spectroscopy could become a powerful tool to highlight electronic dynamics occurring along nonadiabatic chemical reaction pathways. 相似文献
3.
Sansone G Benedetti E Calegari F Vozzi C Avaldi L Flammini R Poletto L Villoresi P Altucci C Velotta R Stagira S De Silvestri S Nisoli M 《Science (New York, N.Y.)》2006,314(5798):443-446
We generated single-cycle isolated attosecond pulses around approximately 36 electron volts using phase-stabilized 5-femtosecond driving pulses with a modulated polarization state. Using a complete temporal characterization technique, we demonstrated the compression of the generated pulses for as low as 130 attoseconds, corresponding to less than 1.2 optical cycles. Numerical simulations of the generation process show that the carrier-envelope phase of the attosecond pulses is stable. The availability of single-cycle isolated attosecond pulses opens the way to a new regime in ultrafast physics, in which the strong-field electron dynamics in atoms and molecules is driven by the electric field of the attosecond pulses rather than by their intensity profile. 相似文献
4.
Reaction path methods provide a powerful tool for bridging the gap between electronic structure and chemical dynamics. Classical mechanical reaction paths may usually be understood in terms of the force field in the vicinity of a minimum energy path (MEP). When there is a significant component of hydrogenic motion along the MEP and a barrier much higher than the average energy of reactants, quantal tunneling paths must be considered, and these tend to be located on the corner-cutting side of the MEP. As the curvature of the MEP in mass-scaled coordinates is increased, the quantal reaction paths may deviate considerably from the classical ones, and the force field must be mapped out over a wider region, called the reaction swath. The required force fields may be represented by global or semiglobal analytic functions, or the dynamics may be computed "directly" from the electronic structure results without the intermediacy of potential energy functions. Applications to atom and diatom reactions in the gas phase and at gas-solid interfaces and to reactions of polyatomic molecules in the gas phase, in clusters, and in aqueous solution are discussed as examples. 相似文献
5.
Kling MF Siedschlag Ch Verhoef AJ Khan JI Schultze M Uphues T Ni Y Uiberacker M Drescher M Krausz F Vrakking MJ 《Science (New York, N.Y.)》2006,312(5771):246-248
We demonstrated how the subcycle evolution of the electric field of light can be used to control the motion of bound electrons. Results are presented for the dissociative ionization of deuterium molecules (D2 --> D+ + D), where asymmetric ejection of the ionic fragment reveals that light-driven intramolecular electronic motion before dissociation localizes the electron on one of the two D+ ions in a controlled way. The results extend subfemtosecond electron control to molecules and provide evidence of its usefulness in controlling reaction dynamics. 相似文献
6.
Goulielmakis E Yakovlev VS Cavalieri AL Uiberacker M Pervak V Apolonski A Kienberger R Kleineberg U Krausz F 《Science (New York, N.Y.)》2007,317(5839):769-775
Electrons emit light, carry electric current, and bind atoms together to form molecules. Insight into and control of their atomic-scale motion are the key to understanding the functioning of biological systems, developing efficient sources of x-ray light, and speeding up electronics. Capturing and steering this electron motion require attosecond resolution and control, respectively (1 attosecond = 10(-18) seconds). A recent revolution in technology has afforded these capabilities: Controlled light waves can steer electrons inside and around atoms, marking the birth of lightwave electronics. Isolated attosecond pulses, well reproduced and fully characterized, demonstrate the power of the new technology. Controlled few-cycle light waves and synchronized attosecond pulses constitute its key tools. We review the current state of lightwave electronics and highlight some future directions. 相似文献
7.
Bucksbaum PH 《Science (New York, N.Y.)》2007,317(5839):766-769
Attoscience is the study of physical processes that occur in less than a fraction of a cycle of visible light, in times less than a quadrillionth of a second. The motion of electrons inside atoms and molecules that are undergoing photoionization or chemical change falls within this time scale, as does the plasma motion that causes the reflectivity of metals. The techniques to study motion on this scale are based on careful control of strong-field laser-atom interactions. These techniques and new research opportunities in attosecond spectroscopy are reviewed. 相似文献
8.
Huismans Y Rouzée A Gijsbertsen A Jungmann JH Smolkowska AS Logman PS Lépine F Cauchy C Zamith S Marchenko T Bakker JM Berden G Redlich B van der Meer AF Muller HG Vermin W Schafer KJ Spanner M Ivanov MY Smirnova O Bauer D Popruzhenko SV Vrakking MJ 《Science (New York, N.Y.)》2011,331(6013):61-64
Ionization is the dominant response of atoms and molecules to intense laser fields and is at the basis of several important techniques, such as the generation of attosecond pulses that allow the measurement of electron motion in real time. We present experiments in which metastable xenon atoms were ionized with intense 7-micrometer laser pulses from a free-electron laser. Holographic structures were observed that record underlying electron dynamics on a sublaser-cycle time scale, enabling photoelectron spectroscopy with a time resolution of almost two orders of magnitude higher than the duration of the ionizing pulse. 相似文献
9.
Wirth A Hassan MT Grguras I Gagnon J Moulet A Luu TT Pabst S Santra R Alahmed ZA Azzeer AM Yakovlev VS Pervak V Krausz F Goulielmakis E 《Science (New York, N.Y.)》2011,334(6053):195-200
Manipulation of electron dynamics calls for electromagnetic forces that can be confined to and controlled over sub-femtosecond time intervals. Tailored transients of light fields can provide these forces. We report on the generation of subcycle field transients spanning the infrared, visible, and ultraviolet frequency regimes with a 1.5-octave three-channel optical field synthesizer and their attosecond sampling. To demonstrate applicability, we field-ionized krypton atoms within a single wave crest and launched a valence-shell electron wavepacket with a well-defined initial phase. Half-cycle field excitation and attosecond probing revealed fine details of atomic-scale electron motion, such as the instantaneous rate of tunneling, the initial charge distribution of a valence-shell wavepacket, the attosecond dynamic shift (instantaneous ac Stark shift) of its energy levels, and its few-femtosecond coherent oscillations. 相似文献
10.
Dynamics of water molecules in aqueous solvation shells 总被引：1，自引：0，他引：1
We report on the direct measurement of the dynamics of water molecules in the solvation shell of an ion in aqueous solution. The hydrogen-bond dynamics of water molecules solvating a Cl-, Br-, or I- anion is slow compared with neat liquid water, indicating that the aqueous solvation shells of these ions are rigid. This rigidity can play an important role in the overall dynamics of chemical reactions in aqueous solution. The experiments were performed with femtosecond midinfrared nonlinear spectroscopy, because this technique allows the spectral response of the water molecules in the solvation shell to be distinguished clearly from that of the other water molecules in the solution. 相似文献
11.
Tunneling electrons from a scanning tunneling microscope (STM) were used to excite photon emission from individual porphyrin molecules adsorbed on an ultrathin alumina film grown on a NiAl(110) surface. Vibrational features were observed in the light-emission spectra that depended sensitively on the different molecular conformations and corresponding electronic states obtained by scanning tunneling spectroscopy. The high spatial resolution of the STM enabled the demonstration of variations in light-emission spectra from different parts of the molecule. These experiments realize the feasibility of fluorescence spectroscopy with the STM and enable the integration of optical spectroscopy with a nanoprobe for the investigation of single molecules. 相似文献
12.
Inelastic electron tunneling spectroscopy is a useful technique for the study of vibrational modes of molecules adsorbed on the surface of oxide layers in a metal-insulator-metal tunnel junction. The technique involves studying the effects of adsorbed molecules on the tunneling spectrum of such junctions. The data give useful information about the structure, bonding, and orientation of adsorbed molecules. One of the major advantages of inelastic electron tunneling spectroscopy is its sensitivity. It is capable of detecting on the order of 10(10) molecules (a fraction of a monolayer) on a 1-square-millimeter junction. It has been successfully used in studies of catalysis, biology, trace impurity detection, and electronic excitations. Because of its high sensitivity, this technique shows great promise in the area of solid-state electronic chemical sensing. 相似文献
13.
A proton shared between two closed-shell molecules, [A.H+.B], constitutes a ubiquitous soft binding motif in biological processes. The vibrational transitions associated with the shared proton, which provide a direct probe of this interaction, have been extensively studied in the condensed phase but have yielded only limited detailed information because of their diffuse character. We exploited recent advances in gas-phase ion spectroscopy to identify sharp spectral features that can be assigned to both the shared proton and the two tethered molecules in a survey of 18 cold, isolated [A.H+.B] ions. These data yield a picture of the intermolecular proton bond at a microscopic scale, facilitating analysis of its properties within the context of a floppy polyatomic molecule. 相似文献
14.
Miller WH 《Science (New York, N.Y.)》1986,233(4760):171-177
15.
Artificial nanostructures, each composed of a copper(II) phthalocyanine (CuPc) molecule bonded to two gold atomic chains with a controlled gap, were assembled on a NiAl(110) surface by manipulation of individual gold atoms and CuPc molecules with a scanning tunneling microscope. The electronic densities of states of these hybrid structures were measured by spatially resolved electronic spectroscopy and systematically tuned by varying the number of gold atoms in the chains one by one. The present approach provides structural images and electronic characterization of the metal-molecule-metal junction, thereby elucidating the nature of the contacts between the molecule and metal in this junction. 相似文献
16.
Even in small molecules, the influence of electronic state on rotational and vibrational product energies is not well understood. Here, we use experiments and theory to address this issue in photodissociation of formaldehyde, H2CO, to the radical products H + HCO. These products result from dissociation from the singlet ground electronic state or the first excited triplet state (T1) of H2CO. Fluorescence spectra reveal a sudden decrease in the HCO rotational energy with increasing photolysis energy accompanied by substantial HCO vibrational excitation. Calculations of the rotational distribution using an ab initio potential energy surface for the T1 state are in very good agreement with experiment and strongly support dominance of the T1 state in the dynamics at the higher photolysis energies. 相似文献
17.
Fluorescence spectroscopy of single biomolecules 总被引：1，自引：0，他引：1
Weiss S 《Science (New York, N.Y.)》1999,283(5408):1676-1683
Recent advances in single-molecule detection and single-molecule spectroscopy at room temperature by laser-induced fluorescence offer new tools for the study of individual macromolecules under physiological conditions. These tools relay conformational states, conformational dynamics, and activity of single biological molecules to physical observables, unmasked by ensemble averaging. Distributions and time trajectories of these observables can therefore be measured during a reaction without the impossible need to synchronize all the molecules in the ensemble. The progress in applying these tools to biological studies with the use of fluorophores that are site-specifically attached to macromolecules is reviewed. 相似文献
18.
Baker S Robinson JS Haworth CA Teng H Smith RA Chirila CC Lein M Tisch JW Marangos JP 《Science (New York, N.Y.)》2006,312(5772):424-427
We demonstrate a technique that uses high-order harmonic generation in molecules to probe nuclear dynamics and structural rearrangement on a subfemtosecond time scale. The chirped nature of the electron wavepacket produced by laser ionization in a strong field gives rise to a similar chirp in the photons emitted upon electron-ion recombination. Use of this chirp in the emitted light allows information about nuclear dynamics to be gained with 100-attosecond temporal resolution, from excitation by an 8-femtosecond pulse, in a single laser shot. Measurements on molecular hydrogen and deuterium agreed well with calculations of ultrafast nuclear dynamics in the H2+ molecule, confirming the validity of the method. We then measured harmonic spectra from CH4 and CD4 to demonstrate a few-femtosecond time scale for the onset of proton rearrangement in methane upon ionization. 相似文献
19.
The dissolution of acids is one of the most fundamental solvation processes, and an important issue is the nature of the hydration complex resulting in ion pair formation. We used femtosecond pump-probe spectroscopy to show that five water molecules are necessary for complete dissolution of a hydrogen bromide molecule to form the contact ion pair H+.Br-(H2O)n in the electronic ground state. In smaller mixed clusters (n < 5), the ion pair formation can be photoinduced by electronic excitation. 相似文献
20.
The dynamics of cesium atom motion above the copper(111) surface following electronic excitation with light was studied with femtosecond (10(-15) seconds) time resolution. Unusual changes in the surface electronic structure within 160 femtoseconds after excitation, observed by time-resolved two-photon photoemission spectroscopy, are attributed to atomic motion in a copper-cesium bond-breaking process. Describing the change in energy of the cesium antibonding state with a simple classical model provides information on the mechanical forces acting on cesium atoms that are "turned on" by photoexcitation. Within 160 femtoseconds, the copper-cesium bond extends by 0.35 angstrom from its equilibrium value. 相似文献