Coherent coupling between vibrational modes of C-H bonds at different positions studied by femtosecond time-resolved coherent anti-Stokes Raman scattering

We performed femtosecond time-resolved coherent anti-Stokes Raman scattering(fs-CARS) measurements on liquid toluene and PVK film.For both samples,we selectively excited the CH stretching vibrational modes and observed the expected quantum beat signals.The frequency of the well-defined beats is in good agreement with the energy difference between the two simultaneously excited modes,which demonstrates that a coherent coupling between the vibrational modes of the C-H chemical bonds exists at the different positions of the molecules.The dephasing times of the excited modes are obtained simultaneously.     

Coherent molecular vibrational dynamics of CH2 stretching modes in polyethylene studied by femtosecond‐CARS

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.     

Theoretical and experimental investigations of coherent phonon dynamics in sapphire crystal using femto- second time-resolved coherent anti-Stokes Raman scattering

We report on the theoretical and the experimental investigations of the coherent phonon dynamics in sapphire crystal using the femtosecond time-resolved coherent anti-Stokes Raman scattering (fs-CARS) technique. The temporal chirped white-light continuum (WLC) is used for the Stokes pulse, therefore we can perform the selective excitation of the phonon modes without using a complicated laser system. The expected quantum beat phenomenon is clearly observed. The theoretical formulas consist very well with the experimental results. The dephasing times of the excited phonon modes, the wavenumber difference, and the phase shift between the simultaneously excited modes are obtained and discussed. This work opens up a way to study directly high-frequency coherent phonon dynamics in bulk crystals on a femtosecond time scale and is especially helpful for understanding the nature of coherent phonons.     

Generation of Vibrational Entangled Coherent States of Two Trapped Ions

We propose a scheme for the generation of entangled coherent states for the center-of-mass and relative vibrational modes of two trapped ions. In the scheme the ions are simultaneously illuminated by a single standing-wave laser tuned to the carrier. The scheme allows the production of an entangled coherent states with a considerably high speed as long as a laser field of sufficiently high intensity is available.     

Generation of Vibrational Entangled Coherent States of Two Trapped Ions

We propose a scheme for the generation of entangled coherent states for the center-of-mass and relative vibrational modes of two trapped ions. In the scheme the ions are simultaneously illuminated by a single standing-wave laser tuned to the carrier. The scheme allows the production of an entangled coherent states with a considerably high speed as long as a laser field of sufficiently high intensity is available.     

Generation of Superpositions of Two-Mode Coherent States for the Motion of Two Trapped Ions

We propose a method for the generation of superpositions of two-mode coherent states for the center-of-mass and relative vibrational modes of two trapped ions. In the scheme the ions are driven by a single travelling-wave laser field tuned to the carrier. Then a measurement of the internal states collapses the vibrational modes to the entangled coherent state.     

液相硝基甲烷分子振动特性的相干反斯托克斯拉曼散射光谱

构建时间分辨相干反斯托克斯拉曼散射（CARS）光谱系统，从微观层次研究硝基甲烷的分子相干振动动力学特性.实验中采用超连续白光作为斯托克斯光，通过调整斯托克斯光的时间延迟，得到不同振动模式的CARS光谱.通过对振动弛豫曲线的拟合，获得硝基甲烷分子不同振动模式的振动失相时间.结果表明C–H键伸缩振动比C–N键伸缩振动更容易受热声子的影响.在热加载下，硝基甲烷分子的C–H键有望首先被激发并引起初始化学反应.     

Generation of Superpositions of Two-Mode Coherent States for the Motion of Two Trapped Ions

We propose a method for the generation of superpositions of two-mode coherent states for the center-of-mass and relative vibrational modes of two trapped ions. In the scheme the ions are driven by a single travelling-wave laser field tuned to the carrier. Then a measurement of the internal states collapses the vibrational modes to the entangled coherent state.     

Femtosecond dynamics of primary processes in visual pigment rhodopsin

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.     

Role of Mode-mode Coupling in Short-time Excited State Decay

Master equation of a relevant electronic and vibrational system is derived for a special diabatic basis corresponding to vertical processes. It is shown that bath modes contribute dynamically to the inter-state coupling only at short times. For long times the bath-induced inter-state coupling is static and increases with the contribution of bath modes to the Stokes shift and to the Herzberg-Teller correction of the excited state. Simultaneously, the time evolution of excited state population is studied numerically for the system consisting of two electronic levels interacting with two vibrational modes, coupled to a heat bath. A mutual coupling of the vibrational modes in the excited state is taken into account (Duschinsky effect). Excited state population relaxes faster if interacting vibrational mode dissipates its energy via vibrational mode of a smaller eigenfrequency. Fast component of excited state depopulation cannot be achieved via coherent mode-mode coupling, if the second mode is not directly coupled to the electronic inter-state transition.