Selective excitation of molecular mode in a mixture by femtosecond resonance-enhanced coherent anti-Stokes Raman scattering spectroscopy

Femtosecond time-resolved coherent anti-Stokes Raman scattering (CARS) spectroscopy is used to investigate gaseous molecular dynamics. Due to the spectrally broad laser pulses, usually poorly resolved spectra result from this broad spectroscopy. However, it can be demonstrated that by the electronic resonance enhancement optimization control a selective excitation of specific vibrational mode is possible. Using an electronically resonance-enhanced effect, iodine molecule specific CARS spectroscopy can be obtained from a mixture of iodine-air at room temperature and a pressure of 1 atm (corresponding to a saturation iodine vapour as low as about 35 Pa). The dynamics on either the electronically excited state or the ground state of iodine molecules obtained is consistent with previous studies (vacuum, heated and pure iodine) in the femtosecond time resolved CARS spectroscopy, showing that an effective method of suppressing the non-resonant CARS background and other interferences is demonstrated.     

Molecular dynamics in low vibrational states investigated by fs time-resolved coherent anti-Stokes Raman spectroscopy technique

The molecular dynamics process is investigated in this paper using a broadband fs time-resolved coherent anti-Stokes Raman spectroscopy (CARS) technique. By varying the timing of laser pulses, low vibrational states are started and studied on both the electronically excited B(³Π_0u⁺) state and ground X(¹Σ_0g⁺) state of iodine in the gas phase at room temperature. According to change the pump wavelength or Stokes pulse as well as the wavelength of the detection window for the CARS signal, dynamics on different potential-energy surfaces can be accessed and detected by the CARS spectroscopy. Results show that the period of the oscillation is decreased for the excited B(³Π_0u⁺) state as the wavelength of the pump pulses is increased, while it is increased for the ground X(¹Σ_0g⁺) state with the increase of the Stokes wavelength.     

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.     

Wave packet dynamics in different electronic states investigated by femtosecond time-resolved four-wave-mixing spectroscopy

This paper reviews results on wave packet dynamics investigated by means of femtosecond time-resolved four-wave-mixing (FWM) spectroscopy. First, it is shown that by making use of the various degrees of freedom which are offered by this technique information about molecular dynamics on different potential-energy surfaces can be accessed and separated from each other. By varying the timing, polarization, and wavelengths of the laser pulses as well as the wavelength of the detection window for the FWM signal, different dynamics are coherently excited and probed by the nonlinear spectroscopy. As a model system we use iodine in the gas phase. These techniques are then applied to more-complex molecules (gas phase: benzene, toluene, a binary mixture of benzene and toluene; solid state: polymers of diacetylene matrix-isolated in single crystals of monomer molecules). Here, ground-state dynamics are investigated first without any involvement of electronically excited states and then in electronic resonance to an absorption transition in the investigated molecules. Signal modulations result which are due to wave packet motion as well as polarization beats between modes in different molecules. Phase and intensity changes yield information about intramolecular vibrational energy redistribution, population decay (T₁), phase relaxation (T₂), and coherence times. Received: 12 October 1999 / Published online: 13 July 2000     

飞秒时间分辨质谱和光电子影像对分子激发态动力学的研究

分子量子态的研究,特别是分子激发态演化过程的研究不仅可以了解分子量子态的基本特性和量子态之间的相互作用,而且可以了解化学反应过程和反应通道间的相互作用.飞秒时间分辨质谱和光电子影像是将飞秒抽运-探测分别与飞行时间质谱和光电子影像相结合的超快谱学方法,为实现分子内部量子态探测,研究分子量子态相互作用及超快动力学过程提供了强有力的工具,可以在飞秒时间尺度下研究单分子反应过程中的光物理或光化学机理.本文详细介绍了飞秒时间分辨质谱和光电子影像的技术原理,并结合本课题组的工作,展示了这两种方法在量子态探测及相互作用研究领域,特别是激发态电子退相、波包演化、能量转移、分子光解动力学以及分子激发态结构动力学研究中的广泛应用.最后,对该技术的发展前景以及进一步的研究工作和方向进行了展望.     

Investigation of molecular dynamics in β-carotene using femtosecond pump-FWM spectroscopy

We have carried out two different pump four-wave mixing experiments, combining an initial pump excitation and a subsequent four-wave mixing probe process, on the photosynthetic pigment β-carotene to reveal different aspects of its molecular dynamics after photoexcitation. Firstly, the pump degenerate four-wave mixing (pump -DFWM) technique, in which the DFWM is resonant with the S₁- to S _n -transition of β-carotene, is used to monitor the events following excitation of the system. The transient shows a peculiar shape and is seen to depend on the energy of the initial pump pulse as well as on the concentration of the solute in the solvent. Secondly, pump coherent anti-Stokes Raman scattering (pump-CARS) is used to elucidate the excited state vibrational dynamics of β-carotene. This technique gives access to the dynamics of both ground and excited electronic states with vibrational selectivity.     

Excitation dynamics of Rydberg states in C<Subscript>60</Subscript>

The electron and nuclear dynamics of C₆₀ fullerenes irradiated with femtosecond laser pulses are investigated with photoelectron and photoion spectroscopy. The focus of this work is the detailed exploration of the population mechanism of Rydberg levels within the excitation process of neutral C₆₀. The effect of excitation wavelength, intensity, chirp, and polarization on the kinetic energy distribution of photoelectrons in single-pulse experiments gives first insight into the underlying processes. In combination with time-resolved two-color pump-probe spectroscopy depending on either pump, or probe pulse intensity, a more complete picture of the interaction can be drawn. The results point towards a very interesting but nevertheless complex behavior including four steps: (i) non-adiabatic multielectron excitation of the HOMO (h_u) → LUMO+1 (t_1g) transition; (ii) thermalization within the hot electron cloud on a time scale below 100 fs, followed by a coupling of energy to vibrational modes of the molecule via doorway state(s); (iii) population of electronically excited Rydberg states by multiphoton absorption, and (iv) single photon ionization from the excited Rydberg states. This excitation process results in a characteristic sequence of photoelectron lines in the photoemission spectra. The comparison of the experimental results with recent theoretical work gives convincing evidence that non-adiabatic multielectron dynamics (NMED) plays a key role for the understanding of the response of C₆₀ to short-pulse laser radiation.     

Vibrational quasicontinuum of polyatomic molecules: New problems for laser spectroscopy

Generally, the subject of the paper is related to the structure of highly excited vibrational states of polyatomic molecules. The problem is treated in terms of intramolecular vibrational dynamics as well as spectroscopy of vibrational transitions. Theoretical approximations which allow us to calculate spectra starting from dynamics are discussed. A microscopic treatment of spectroscopic relaxation timesT ₁ andT ₂ is given. Also, various experimental approaches to study the problem are outlined including the measurements of stochasticity onset in molecules.     

飞秒时间分辨拉曼光谱用于研究β-胡萝卜素单重激发态内转换和振动弛豫过程

搭建了飞秒时间分辨受激拉曼光谱(FSRS)装置,并用于研究全反式β-胡萝卜素单重电子激发态超快内转换和振动弛豫过程.基于三脉冲“抽运-探测”方案搭建的时间分辨受激拉曼光谱装置同时实现了150fs的时间分辨率和23.7cm^-1的光谱分辨率,光谱检测范围为300—4000cm^-1.对全反式β-胡萝卜素电子激发态的飞秒时间分辨拉曼光谱研究表明,β-胡萝卜素被激发到S₂态后,经由寿命约为0.3ps的中间态S_X态实 关键词： 飞秒时间分辨拉曼光谱 β-胡萝卜素 激发态内转换 振动弛豫     

Observation of rotational energy transfer in iodine by two-photon time delayed spectroscopy

The temporal evolution for individual rovibrational levels of the B state of the iodine molecule is observed by two-photon delayed spectroscopy. In particular the rotational energy transfer (RET) process due to collisions of the molecules in the B state with molecules in the ground state is studied. Thermal averaged rate constants for pairs of rotational levels of the v=27 vibrational state are measured. The results are discussed in terms of the dynamics of the collision process and numerical fits to the most important parametric fitting laws for RET are presented.     

Intra-acceptor hole relaxation in Be δ-doped GaAs/AlAs multiple quantum wells

This paper studies the dynamics of intra-acceptor hole relaxation in Be δ -doped GaAs/AlAs multiple quantum wells (MQW) with doping at the centre by time-resolved pump-probe spectroscopy using a picosecond free electron laser for infrared experiments. Low temperature far-infrared absorption measurements clearly show three principal absorption lines due to transitions of the Be acceptor from the ground state to the first three odd-parity excited states respectively. The pump-probe experiments are performed at different temperatures and different pump pulse wavelengths. The hole relaxation time from 2p excited state to 1s ground state in MQW is found to be much shorter than that in bulk GaAs, and shown to be independent of temperature but strongly dependent on wavelength. The zone-folded acoustic phonon emission and slower decay of the wavefunctions of impurity states are suggested to account for the reduction of the 2p excited state lifetime in MQW. The wavelength dependence of the 2p lifetime is attributed to the diffusion of the Be atom δ -layer in quantum wells.     

Calculation and interpretation of vibronic absorption and fluorescence spectra of the first electronic nπ* transitions of pyridine and pyrimidine

We have calculated vibronic spectra of the first electronic nπ* transitions of pyridine and pyrimidine in the isolated state using the DFT method in the Franck-Condon approximation. Vibrational spectra for the ground and excited states have been calculated in the anharmonic approximation, which allowed us to refine the assignment of normal vibrations of pyridine and pyrimidine. We have done a complete interpretation of the vibrational structure of the absorption and fluorescence spectra of pyridine and pyrimidine. It has been shown that Fermi resonances between fundamental and combination vibrations and overtones 12 and 16b + 4, 6a and 2 × 16b affect the formation of the vibrational structure of electronic spectra of pyrimidine. Good agreement between calculated and experimental spectra confirms the correctness of the models of the two molecules in their ground and excited states, which makes it possible to use the models in further investigations of various properties of these molecules in electronically excited states, e.g., tautomerism of pyrimidine bases of nucleic acids.     

Electronic excitation and thermal effects in alkali-halide cluster anions

We have observed electronically excited states in alkali-halide cluster anions with one excess electron. Using photoelectron spectroscopy, we have found two narrow states in (KI)-2, (NaI)-2, and (NaCl)-2, consistent with a dipole-bound electron, while larger cluster anions exhibit a single broad excited state. In the larger systems, electronic excitation is often accompanied by vibrational excitation and thus a change in cluster temperature. Such temperature changes affect cluster structure and in some cases lead to rapid thermal isomerization.     

强红外场作用下BCl3振动态传能动力学研究

基于文献[1],本工作在较高泵浦激光能通量范围,测量并研究了BCl₃分子振动激发v_3吸收谱及时间演变,观察了v₃激发弛豫的几种能量转移过程,以及对泵浦激光能量BCl₃气压等参数的依赖关系。表明泵浦光脉冲产生一个振动态非热分布的系综,转动能量转移对引起这种非热分布有重要作用。用简化碰撞动力学模型讨论了BCl₃振动激发吸收谱的演变过程,得到振动态再分布的简单关系;Pτ_v-v≌c/K′(T_v,T₀,q)和等效振动温度、平均吸收光子数的分析表达式,与实验结果定性地符合。 关键词：     

Rapid internal conversion in a symmetric molecule LD 700 studied by means of femtosecond fluorescence depletion

The rapid internal conversion dynamics at room temperature is determined by using the femtosecond time-resolved fluorescence depletion measurements of a complex solvated molecule of LD 700 (rhodamine 700) combined with steady-state absorption and fluorescence spectroscopy, as well as quantum chemical calculation. The molecule is excited by a 50fs laser pulse at 400nm which directly populated the highly excited singlet state, the rapid internal conversions (ICs) are observed, which leads to the directional changes of the emission transition moment following photoexcitation to the highly excited singlet state S₅ of LD 700.     

Ab initio SCF CI study of the electronic spectrum of s-tetrazine

Configuration interaction (CI) studies of ground, n→ π* and π→ π* electronically excited states are reported for s-tetrazine. The first n→ π* singlet excited state (¹ B _3u ), which is responsible for the purple-red colour of the molecule, is calculated at 2·80 eV, compared to the experimental transition energy of 2·22–2·70 eV. The singlet-triplet split of the first n→ π* states (¹ B _3u and ³ B _3u states) is calculated to be 0·76 eV.

The interaction of nitrogen lone pair orbitals (n-orbitals) is studied in terms of the ordering of the n π* excited states and found that the SCF orbital ordering is qualitatively in accord with the ordering of the n π* excited states in the CI level.

The first π→ π* excited state (¹ B _2u ) is calculated at 5·99 eV, slightly above the observed range of absorption. Numerous other high-lying singlet states as well as the triplet states have been calculated and they are used to verify several proposals relating to the excited state dynamics in the photo-physical studies of s-tetrazine.     

Optical diagnostics for temperature measurement in a DC arcjet reactor used for diamond deposition

2 a-state in this plume. LIF measurements of CH are complicated by the presence of C₃ and we discuss strategies to deal with this interference. The gas temperature describing the rotational distributions obtained for NO, C₂ and CH agree within experimental error. Optical emission measurements indicate that the rotational and vibrational distributions of the excited A-state of CH and a-state of C₂ are characterized by vibrational and rotational populations which are at least 1000 K above the ground state distributions. The excited states are collisionally quenched before their population distributions equilibrate with the gas temperature. We also determine relative populations of the ground and excited states along the axis of the plume between the arcjet nozzle and the substrate and relative populations for a cross section of the jet, midway between the nozzle orifice and the substrate. The measured relative ground and excited state populations for both CH and C₂ show different trends along the plume axis, indicating that the ground and excited states of these molecules are products of different chemical mechanisms; such mechanisms are discussed. Received: 16 July 1996/Revised version: 24 September 1996     

A quasiclassical study of collisions of He with HD(B 1Σ+ u )

A quasiclassical trajectory study has been carried out for collisions of ⁴He with electronically excited H₂(B ¹Σ⁺ _u ) and its isotopomer HD. By using analytical fits for the ab initio potential energy surfaces of the ground and the excited state we have obtained vibrational and electronic quenching cross sections for several initial conditions. We draw the following conclusions. Vibrational excitation strongly promotes electronic quenching whereas translational energy is less effective. Rotational excitation decreases the rate of quenching. In a remarkable contrast to the ground electronic state, vibrational energy transfer on the excited potential energy surface is an efficient and fast process. Collisions at high energies results in T → R energy transfer. The above conclusions are valid for both H₂ and HD.     

N-乙基吡咯S1态超快动力学：飞秒时间分辨光电子成像研究

N-乙基吡咯是吡咯分子的一个乙基取代衍生物,它的激发态衰变动力学目前为止很少被研究. 本文利用飞秒时间分辨光电子成像的实验方法研究N-乙基吡咯分子S₁态的衰变动力学. 实验采用241.9和237.7 nm的泵浦激发波长. 在241.9 nm激发下,得到5.0±0.7 ps,66.4±15.6 ps和1.3±0.1 ns三个寿命常数. 在237.7 nm激发下,得到2.1±0.1 ps和13.1±1.2 ps两个寿命常数. 所有寿命常数都归属为S₁态的振动态. 本文并对不同S₁振动态的弛豫机理进行了讨论.