共查询到20条相似文献,搜索用时 25 毫秒
1.
We study the vibrational dynamics of nanodroplets of liquid water with femtosecond two-color midinfrared pump-probe spectroscopy. For the smallest nanodroplet, containing 10-15 water molecules, the lifetime T1 of the O-H stretch vibrations is equal to 0.85+/-0.1 ps, which is more than 3 times as long as in bulk liquid water. We find that the truncation of the hydrogen-bond network of water leads to a dramatic change of the relaxation mechanism. 相似文献
2.
Hsieh CS Campen RK Vila Verde AC Bolhuis P Nienhuys HK Bonn M 《Physical review letters》2011,107(11):116102
We report the real-time measurement of the ultrafast reorientational motion of water molecules at the water-air interface, using femtosecond time- and polarization-resolved vibrational sum-frequency spectroscopy. Vibrational excitation of dangling OH bonds along a specific polarization axis induces a transient anisotropy that decays due to the reorientation of vibrationally excited OH groups. The reorientation of interfacial water is shown to occur on subpicosecond time scales, several times faster than in the bulk, which can be attributed to the lower degree of hydrogen bond coordination at the interface. Molecular dynamics simulations of interfacial water dynamics are in quantitative agreement with experimental observations and show that, unlike in bulk, the interfacial reorientation occurs in a largely diffusive manner. 相似文献
3.
The dynamical behavior of excess protons in liquid water is investigated using femtosecond vibrational pump-probe spectroscopy. By resonantly exciting the O-H+-stretching mode of the H9O4(+) (Eigen) hydration structure of the proton and probing the subsequent absorption change over a broad frequency range, the dynamics of the proton is observed in real time. The lifetime of the protonic stretching mode is found to be approximately 120 fs, shorter than for any other vibration in liquid water. We also observe the interconversion between the H9O4(+) (Eigen) and H5O2(+) (Zundel) hydration structures of the proton. This interconversion, which constitutes an essential step of proton transport in water, is found to occur on an extremely fast (< 100 fs) time scale. 相似文献
4.
Takanori Kozai Yuya Kayano Takahito Aoi Noriaki Tsurumachi Shunsuke Nakanishi 《Journal of Raman spectroscopy : JRS》2015,46(4):384-387
We have studied the coherent molecular vibrational dynamics of CH2 stretching modes in polyethylene by time‐resolved femtosecond coherent anti‐Stokes Raman spectroscopy. We observed that the coherent vibrational relaxation of symmetric CH2 stretching modes in polyethylene at room temperature is much faster than that previously measured in polyvinyl alcohol. In addition, it was detected that, at low temperature, the coherent vibrational relaxation of the symmetric stretching modes evidently becomes slower compared with that at room temperature. These temperature‐dependent measurements enable us to discriminate the contribution of pure dephasing mechanism, due to phonons and two‐level systems in polymer, from the contribution of lifetime of the vibrational excited state to the coherent vibrational relaxation of CH2 stretching modes. We conclude that the coherent vibrational relaxation of symmetric CH2 stretching modes at room temperature consists of the contribution of lifetime and approximately 1.5 times larger contribution of pure dephasing. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
5.
Bruchhausen A Gebs R Hudert F Issenmann D Klatt G Bartels A Schecker O Waitz R Erbe A Scheer E Huntzinger JR Mlayah A Dekorsy T 《Physical review letters》2011,106(7):077401
We propose subharmonic resonant optical excitation with femtosecond lasers as a new method for the characterization of phononic and nanomechanical systems in the gigahertz to terahertz frequency range. This method is applied for the investigation of confined acoustic modes in a free-standing semiconductor membrane. By tuning the repetition rate of a femtosecond laser through a subharmonic of a mechanical resonance we amplify the mechanical amplitude, directly measure the linewidth with megahertz resolution, infer the lifetime of the coherently excited vibrational states, accurately determine the system's quality factor, and determine the amplitude of the mechanical motion with femtometer resolution. 相似文献
6.
Ultrafast hot-electron dynamics observed in Pt( -)(3) using time-resolved photoelectron spectroscopy
Time-resolved two-photon photoelectron spectra have been measured for free Pt( -)(3) using femtosecond pulses of 1.5 eV photon energy in a pump-probe configuration. The time-dependent photoelectron distribution reveals a lifetime of optically excited states of less than 70 fs. Such an unexpected fast electron relaxation in Pt( -)(3) suggests the existence of inelastic electron-electron scattering processes in a triatomic cluster which result in a lifetime similar to those of bulk metals. 相似文献
7.
《Current Applied Physics》2015,15(11):1492-1499
1,2-Dihydroxyanthraquinone (alizarin) shows dual emission bands with a large Stokes shift from a “locally-excited (LE)” and “proton-transferred (PT)” tautomers in the excited state. Excited state intramolecular proton transfer (ESIPT) reaction of alizarin is tunable by changing concentration, solvent polarity, excitation wavelength, and etc. ESIPT reaction of alizarin in the excited state was investigated by steady-state absorption/emission spectroscopy and femtosecond transient absorption spectroscopy. In ethanol solution, the lifetime of PT tautomer of alizarin was measured as 87 ps, in addition to 0.35 and 8.3 ps vibrational cooling dynamics for the LE and PT tautomers of alizarin, respectively. In binary mixtures of ethanol and water, the excited state dynamics became more complicated; the LE and PT tautomers appeared to decay with 8.9 and 30.8 ps lifetimes, which is much shorter compared to the lifetime of the PT tautomer in ethanol. A long-lived nonradiative state in the excited states of alizarin was found as well, which was proposed as a “trapped” state with tightly hydrogen-bonded water molecules. The ESIPT reaction of alizarin was blocked in a 1:1 mixture of ethanol-water due to strong hydrogen bonding between water molecules and alizarin, which was further confirmed by the efficient coupling of alizarin to TiO2 nanoparticles in the 1:1 binary mixture of ethanol-water. 相似文献
8.
The dynamics of water, confined on a nanometer length scale (1.7 to 4.0 nm) in sodium bis-(2-ethylhexyl) sulfosuccinate reverse micelles, is directly investigated using frequency resolved infrared vibrational echo experiments. The data are compared to bulk water and salt solution data. The experimentally determined frequency-frequency correlation functions show that the confined water dynamics is substantially slower than bulk water dynamics and is size dependent. The fastest dynamics (approximately 50 fs) is more similar to bulk water, while the slowest time scale dynamics is much slower than water, and, in analogy to bulk water, reflects the making and breaking of hydrogen bonds. 相似文献
9.
Israel Rocha‐Mendoza Paola Borri Wolfgang Langbein 《Journal of Raman spectroscopy : JRS》2013,44(2):255-261
We demonstrate a technique for simultaneous detection of coherent anti‐Stokes Raman scattering (CARS) at four vibrational frequencies, using simple passive optical elements and without spectrally resolved detection. The technique is based on pump and Stokes femtosecond pulses selectively exciting vibrational resonances through spectral focusing. By replicating the pump and Stokes pair into four pairs, each traveling through appropriate glass elements, we simultaneously excite four different vibrational frequencies. The resulting CARS is a periodic train of intensities detected by a single photomultiplier and frequency analyzed to retrieve its Fourier coefficients. We demonstrate detection of methanol and ethanol mixtures in water and quantitative determination of their concentration owing to the improved chemical selectivity of this quadruplex CARS scheme. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
10.
Brena B Nordlund D Odelius M Ogasawara H Nilsson A Pettersson LG 《Physical review letters》2004,93(14):148302
Using x-ray emission and photoemission spectroscopies to measure the occupied valence levels in a thin crystalline ice film, we resolve the ionization-induced dissociation of water in ice on a femtosecond time scale. Isotope substitution confirms proton transfer during the core-hole lifetime in spite of the nonresonant excitation. Through ab initio molecular dynamics on the core-ionized state, the dissociation and spectrum evolution are followed at femtosecond intervals. The theoretical simulations confirm the experimental analysis and allow for a detailed study of the dissociative reaction path. 相似文献
11.
Naveen Kumar Kaliannan Andres Henao Aristizabal Hendrik Wiebeler Frederik Zysk Tatsuhiko Ohto Yuki Nagata 《Molecular physics》2020,118(4)
ABSTRACTWe have examined the impact of intermolecular vibrational coupling effects of the O-H stretch modes, as obtained by the surface-specific velocity-velocity correlation function approach, on the simulated sum-frequency generation spectra of the water/air interface. Our study shows that the inclusion of intermolecular coupling effects within the first three water layers, i.e. from the water/air interface up to a distance of 6?Å towards the bulk, is essential to reproduce the experimental SFG spectra. In particular, we find that these intermolecular vibrational contributions to the SFG spectra of the water/air interface are dominated by the coupling between the SFG active interfacial and SFG inactive bulk water molecules. Moreover, we find that most of the intermolecular vibrational contributions to the spectra originate from the coupling between double-donor water molecules only, whereas the remaining contributions originate mainly from the coupling between single-donor and double-donor water molecules. 相似文献
12.
Sung-Hak Cho Won-Seok Chang Kwang-Ryul Kim Jong Wook Hong 《Optics and Lasers in Engineering》2009,47(1):127-132
Time-resolved dynamics of plasma formation and bulk refractive-index modification in fluoride glass (ZBLAN) excited by a tightly focused femtosecond (130 fs) Ti:sapphire laser (λp=790 nm) was observed in situ. The femtosecond time-resolved pump–probe measurement with perpendicularly linear polarized beams was used to study the dynamics of both plasma formation and induced permanent structural transformation with refractive-index change. In the refractive-index domain, the lifetime of induced plasma formation is ~35 ps and structural transition time for forming the refractive-index change is ~80 ps. In the optical damage domain, however, the lifetime of induced plasma formation is ~40 ps and structural transition time for forming the optical damage is ~140 ps. We found that the process of refractive-index bulk modification is significantly different from that of optical cracks. From the diffraction efficiency of Kogelnik's coupled mode theory, the maximum value of refractive-index change (Δn) was estimated to be 1.3×10?2. By the scanning of fluoride glass on the optical X–Y–Z stages, the fabrication of internal grating with refractive-index modification was demonstrated in fluoride glass using tightly focused femtosecond laser. 相似文献
13.
I. V. Shelaev M. N. Mozgovaya O. A. Smitienko F. E. Gostev T. B. Fel’dman V. A. Nadtochenko O. M. Sarkisov M. A. Ostrovskii 《Russian Journal of Physical Chemistry B, Focus on Physics》2014,8(4):510-517
The dynamics of the coherent photoisomerization of the 11-cis-retinal in bovine rhodopsin is studied by femtosecond time-resolved laser absorption spectroscopy with a resolution of 30 fs. Rhodopsin is excited with 500-, 535-, and 560-nm femtosecond pulses to produce different initial Franck-Condon states with different vibrational energies of the molecule in its electronically excited state. The time evolution of the photoinduced differential absorption spectra of rhodopsin is measured upon excitation with a femtosecond pulse in a spectral range from 400 to 720 nm. Oscillations in the time-resolved absorption of the rhodopsin photoproducts, such as photorhodopsin with a vibrationally excited all-trans-retinal and in its initial-state rhodopsin with a vibrationally excited 11-cis-retinal, are examined. It is demonstrated that these oscillations reflect the dynamics of coherent vibrational wavepackets. The Fourier transform of these oscillatory components yields frequencies, amplitudes, and initial phases of various vibrational modes involved in the motion the wavepackets in both photoproducts. The main vibrational modes manifest themselves at frequencies of 62 and 160 cm?1 for photorhodopsin and 44 and 142 cm?1 for initial-state rhodopsin. It is shown that these vibrational modes are directly involved in the coherent reaction under the study, with their amplitudes in the power spectrum produced by the Fourier transform of the kinetic curves being dependent on the wavelength of rhodopsin excitation. 相似文献
14.
We have used femtosecond midinfrared spectroscopy to study the orientational mobility of water molecules in the hydration shells of hydrophobic groups. Our results show that hydrophobic groups are surrounded by a number of water molecules that display much slower orientational dynamics than the bulk liquid and that are therefore effectively immobilized. It turns out that each methyl group is surrounded by four immobilized water OH groups. 相似文献
15.
R.W. Schoenlein S. Chattopadhyay H.H.W. Chong T.E. Glover P.A. Heimann W.P. Leemans C.V. Shank A. Zholents M. Zolotorev 《Applied physics. B, Lasers and optics》2000,71(1):1-10
The generation of femtosecond X-ray pulses will have important scientific applications by enabling the direct measurement of atomic motion and structural dynamics in condensed matter on the fundamental time scale of a vibrational period. Interaction of femtosecond laser pulses with relativistic electron beams is an effective approach to generating femtosecond pulses of X-rays. In this paper we present recent results from proof-of-principle experiments in which 300 fs pulses are generated from a synchrotron storage ring by using an ultrashort optical pulse to create femtosecond time structure on the stored electron bunch. A previously demonstrated approach for generating femtosecond X-rays via Thomson scattering between terawatt laser pulses and relativistic electrons is reviewed and compared with storage-ring based schemes. 相似文献
16.
17.
18.
Xin Du Xing He Yunfei Song Yang Wang Yuqiang Liu Lilin Jiang Mingfu Zhang Yanqiang Yang 《Optics & Laser Technology》2012,44(5):1324-1327
We have studied the quantum beats of vibrational modes in different phase samples by employing femtosecond time-resolved coherent anti-Stokes Raman scattering (fs-CARS) technique. The temporal chirped white-light continuum (WLC) is used for the Stokes pulse, we have achieved the selective excitation of vibrational modes in both the low and high wavenumber regions without complicated laser system, and observed quantum coherence between vibrational modes. This work is of special significance to enhance our understanding of quantum coherence and develop the applications of quantum technologies. 相似文献
19.
The application of femtosecond pump-probe photoelectron spectroscopy to directly observe vibrational wave packets passing through an avoided crossing is investigated using quantum wave packet dynamics calculations. Transfer of the vibrational wave packet between diabatic electronic surfaces, bifurcation of the wave packet, and wave packet construction via nonadiabatic mixing are shown to be observable as time-dependent splittings of peaks in the photoelectron spectra. 相似文献
20.
Malinovskaya SA 《Optics letters》2008,33(19):2245-2247
We study the vibrational energy relaxation (VER) and collisional dephasing as channels of coherence loss in a vibrational mode that is selectively excited using chirped pulse adiabatic passage in the Raman configuration. Based on the dressed state picture analysis we propose a method to reduce decoherence using femtosecond chirped pulse trains. When applied with a period close to the VER time, the pulse trains allow one to sustain high coherence in the selected vibrational mode. 相似文献