Decoupling multimode vibrational relaxations in multi-component gas mixtures: Analysis of sound relaxational absorption spectra

Decoupling the complicated vibrational-vibrational （V-V） coupling of a multimode vibrational relaxation remains a challenge for analyzing the sound relaxational absorption in multi-component gas mixtures. In our previous work [Acta Phys. Sin. 61 174301 （2012）], an analytical model to predict the sound absorption from vibrational relaxation in a gas medium is proposed. In this paper, we develop the model to decouple the V-V coupled energy to each vibrationaltranslational deexcitation path, and analyze how the multimode relaxations form the peaks of sound absorption spectra in gas mixtures. We prove that a multimode relaxation is the sum of its decoupled single-relaxation processes, and only the decoupled process with a significant isochoric-molar-heat can be observed as an absorption peak. The decoupling model clarifies the essential processes behind the peaks in spectra arising from the multimode relaxations in multi-component gas mixtures. The simulation validates the proposed decoupling model.

Photo-induced intramolecular electron transfer and intramolecular vibrational relaxation of rhodamine 6G in DMSO revealed by multiplex transient grating spectroscopy

Photo-induced intramolecular electron transfer （PIET） and intramolecular vibrational relaxation （IVR） dynamics of the excited state of rhodamine 6G （Rh6G＋） in DMSO are investigated by multiplex transient grating. Two major compo- nents are resolved in the dynamics of Rh6G＋. The first component, with a lifetime τTPIET = 140 fs-260 fs, is attributed to PIET from the phenyl ring to the xanthene plane. The IVR process occurring in the range ZIVR = 3.3 ps-5.2 ps is much slower than the first component. The PIET and IVR processes occurring in the excited state of Rh6G＋ are quantitatively determined, and a better understanding of the relationship between these processes is obtained.

Study of vibrational relaxation of O_3 (001)using photoacoustic technique

The vibration- translational relaxation ime of ozone (001) was measured from phase delay of the photoacoustic detected signal with respect to signal of CO2-laser radiation in the binary mixtures of O3 with N2, O2, and Ar at the temperature 300°K. To eliminate the phase delay of the detected signal caused by inertia of the microphone membrane the technique of electrical activation was used.

Intramolecular vibrational dynamical barrier due to extremely irrational couplings

The intramolecular vibrational dynamics due to extremely irrational couplings is demonstrated by contrast to the resonance couplings, for the three-mode case of H2O as an example. The extremely irrational couplings are shown to impose such strong hindrance to intramolecular vibrational relaxation （IVR） that they act as barriers. They restrict the direct action/energy transfer between the two stretching modes, though they allow the transfer between a stretching and a bending modes. In contrast, the resonance is more mediated by the bending mode and leads to chaotic IVR. It is also shown that there is a region in the dynamical space in which resonance and extremely irrational couplings coexist.

Electron-Vibrational Energy Exchange in Nitrogen-Containing Plasma:a Comparison Between an Analytical Approach and a Kinetic Model

This paper investigates the electron-vibrational（e-V）energy exchange in nitrogencontaining plasma,which is very efficient in the case of gas discharge and high speed flow.Based on Harmonic oscillator approximation and the assumption of the e-V relaxation through a continuous series of Boltzmann distributions over the vibrational states,an analytic approach is derived from the proposed scaling relation of e-V transition rates.A full kinetic model is then investigated by numerically solving the state-to-state master equation for all vibrational levels.The analytical approach leads to a Landau-Teller（LT）-type equation for relaxation of vibrational energy,and predicts the relaxation time on the right order of magnitude.By comparison with the kinetic model,the LT-type equation is valid in typical electron temperatures in gas discharge.However,the analytical approach is not capable of describing the vibrational distribution function during the e-V process in which a full kinetic model is required.

Kinetics of Hydrogen Molecules in MAGNUM-PSI

Results from simulations of plasma and neutrals under conditions predictively characterizing the detached plasma regime in the linear machine MAGNUM-PSI are presented. The relaxation of the vibrationally excited hydrogen molecules is investigated in order to establish a relation between their relaxation and dwell times, and the role of the varions mechanisms of the molecular vibrational kinetics. Tile results obtained show that the individual vibrational states have to be inclllded in the transport code for neutrals as distinct species, since the relaxation time of tile vibrational states is sufficiently longer than the typical dwell time of hydrogen molecules in the detached plasma region. The parameters of plasma and neutrals are affected by the transport of the vibrationally excited hydrogen lnolecnles. Furthermore. the rate of molecular reconlbination is overestimated by a factor of - 5 provided that the transport of ilydrogen molecules only in their ground vibrational state is considered. The role of the various processes of vibrational kinetics is studied. The vibrational excitation through singlet electronic states ires a strong influence on the molecular densities for levels with vibrational quantum numbers v≥ 5. Vibration-vibration （V-V） collisions between vibrationally excited hydrogen molecules and vibration-translation （V-T） collisions between vibrationally excited hydrogen molecules and ground state molecules and atoms are of nlinor importance in MAGNUM-PSI.

Ultrafast proton transfer dynamics of 2-(2'-hydroxyphenyl)benzoxazole dye in different solvents

The excited-state intramolecular proton transfer of 2-(2-hydroxyphenyl)benzoxazole dye in different solvents is investigated using ultrafast femtosecond transient absorption spectroscopy combined with quantum chemical calculations.Conformational conversion from the syn-enol configuration to the keto configuration is proposed as the mechanism of excited-state intramolecular proton transfer.The duration of excited-state intramolecular proton transfer is measured to range from 50 fs to 200 fs in different solvents.This time is strongly dependent on the calculated energy gap between the N-S;and T-S;structures in the S;state.Along the proton transfer reaction coordinate,the vibrational relaxation process on the S;state potential surface is observed.The duration of the vibrational relaxation process is determined to be from8.7 ps to 35 ps dependent on the excess vibrational energy.

Periodic thermodynamics of laser-driven molecular motor

Operation of a laser-driven nano-motor inevitably generates a non-trivial amount of heat, which can possibly lead to instability or even hinder the motor＇s continual running. This work quantitatively examines the overheating problem for a recently proposed laser-operated molecular locomotive. We present a single-molecule cooling theory, in which molecular details of the locomotive system are explicitly treated. This theory is able to quantitatively predict cooling efficiency for various candidates of molecular systems for the locomotive, and also suggests concrete strategies for improving the locomotive＇s cooling. It is found that water environment is able to cool the hot locomotive down to room temperature within 100 picoseconds after photon absorption. This cooling time is a few orders of magnitude shorter than the typical time for laser operation, effectively preventing any overheating for the nano-locomotive. However, when the cooling is less effective in non-aqueous environment, residual heat may build up. A continuous running of the motor will then lead to a periodic thermodynamics, which is a common character of many laser-operated nano-devices.

Calculation of vibrational energy transition rates in acoustic relaxation processes for excitable gas molecules

To research the correlation between vibrational energy transition rates and acoustic relaxation processes in excitable gases, the vibrational relaxation theory provided by Tanczos [J. Chem. Phy3. 25, 439 （1956）] is applied to calculate the energy transition rates of Vibrational- Vibrational （V-V） and Vibrational-Translational （V-T） energy transfer in gas mixtures. The results of calculation for the multi-relaxation processes in various gas mixtures, consisting of carbon dioxide, methane, chlorine, nitrogen, and oxygen at room temperature, demonstrate that the acoustic energy stagnated in every vibrational mode is coupled with each other through V-V energy exchanges. The vibrational excitation energy will relax through the V-T de-excitation path of the lowest mode because of its fastest V-T transition rate, resulting in that only one absorption peak can be measured for most of excitable gas mixtures. Thus, an effective model is provided to analyze how the vibrational energy transition rates affect the characteristics of acoustic relaxation processes and acoustic propagation in excitable gas mixtures.

Molecular mechanism of aggregation-induced emission

Deep understanding of the inherent luminescence mechanism is essential for the development of aggregation-induced emission(AIE)materials and applications.We first note that the intermolecular excitonic coupling is much weaker in strength than the intramolecular electron-vibration coupling for a majority of newly termed AIEgens,which leads to the emission peak position insensitive to excitonic coupling,hence the conventional excitonic model for J-aggregation cannot effectively explain their AIE phenomena.Then,using multiscale computational approach coupled with our self-developed thermal vibration correlation function rate formalism and transition-state theory,we quantitatively investigate the aggregation effect on both the radiative and the nonradiative decays of molecular excited states.For radiative decay processes,we propose that the lowest excited state could convert from a transition dipole-forbidden“dark”state to a dipole-allowed“bright”state upon aggregation.For the radiationless processes,we demonstrate the blockage of nonradiative decay via vibration relaxation(BNR-VR)in harmonic region or the removal of nonradiative decay via isomerization(RNR-ISO)or minimum energy crossing point(RNR-MECP)beyond harmonic region in a variety of AIE aggregates.Our theoretical work not only justifies a plethora of experimental results but also makes reliable predictions on molecular design and mechanism that can be experimentally verified.Looking forward,we believe this review will benefit the deep understanding about the universality of AIE phenomenon and further extending the scope of AIE systems with novel applications.