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.     

The Influence of Temperature on Coumarin 153 Fluorescence Kinetics

The influence of temperature varied in the range 183 K–323 K on the fluorescence quantum yield, fluorescence lifetime, absorption and emission transition moments and non-radiative deactivation rate was determined for the well known and largely used dye Coumarin 153, dissolved in 1-chloropropane. The Kennard-Stepanov relation connecting the absorption and emission spectra was used to check for the presence of more than one absorbing/emitting species and to investigate whether intramolecular vibrational redistribution completes in the C153 excited S ₁ state before the emission takes place. The emission spectrum corresponding to S ₁→S ₀ transition, was fitted at each temperature to the model function including the information on the dye vibrational modes coupling. In this way the displacement in equilibrium distance for the most active vibrational mode was determined for C153 in S ₁ and in S ₀. Using the temperature dependence of the fluorescence decay time and quantum yield, the non-radiative deactivation rate was determined. Its temperature dependence was compared to that calculated using the theoretical model with the most active vibrational mode displacement values taken from steady-state spectra analysis. The somewhat surprising dependence of the fluorescence decay time and quantum yield on temperature was related to non-trivial coupling between low-frequency vibrational modes of C153 in the excited and ground states.     

低振动激发HeI2分子振动预离解寿命和终转动态分布

用含时黄金规则波包法，对ＨｅＩ２分子在低初始振动激发（ｖ＜１２）态下振动预离解动力学作了全维量子力学计算。所预言的总衰变宽度和寿命与谱线宽和皮秒时间分解的实时态－态测量外推数据符合得相当好。计算的总衰变宽度对初始振动态ｖ是敏感的并呈现一种非线性关系。结果表明低振动激发ＨｅＩ２分子衰变模式仍应是量子力学的。除终态相互作用对决定终转动分布有重要作用以外，首次发现，低振动激发态的初始特性也能显著影响终转动态分布。用Ｉ２的转动常数对ｖ的关系合理地解释了这个独特现象     

A theoretical study of energy transfer in the quenching of O(1 D 2) by CO(1Σ+)

Energy transfer processes occurring during the collisional quenching of O(¹ D) by CO(¹Σ⁺) are studied using a classical collision complex model together with potentials previously derived for the C(³ P) + O₂(³Σ _g ^-) reaction. Room temperature quenching rate constants, electronic-vibrational transfer efficiencies and product vibrational state distributions are in good agreement with experiment. The calculated and experimental temperature dependences of the electronic-vibrational transfer efficiencies and vibrational populations, however, disagree. The effect of using vibrationally excited CO as a quenching partner is studied and shown to result in a lowering of the quenching rate constant by a factor of 4 at room temperature. Enhancement of initial translational energy by the equivalent of a vibrational quantum of energy leads to an even larger decrease in the rate constant. This difference between vibrational and translational energy enhancement is interpreted in terms of an increased centrifugal barrier in the latter case.     

Storage of Entangled States with Multiple Trapped Ions in Thermal Motion

This paper presents an alternative scheme to realize the storage of entangled states for multiple trapped ions including W state, Bell states, and GHZ states even with ions which exchange vibrational energy with a heating surrounding. Our scheme requires that the ions be simultaneously excited by two laser beams with different frequencies.In this scheme the vibrational degrees of freedom are only regarded as intermediate states and the ions exchange energy via the mediation of the vibration of the vibrational mode in coupling processes. The scheme is insensitive to both the initial vibrational state and heating if the system remains in the Lamb-Dicke regime. Since the effective Rabi frequency has a small dependence on the vibrational quantum number the heating will have no direct effect on the internal state evolution.     

CARS spectra of thermally excited SF6 molecules

CARS spectra of thev ₁ mode of thermally excited SF₆ were calculated numerically. The influence of the vibrational quasicontinuum on the CARS spectra has been considered by introducing different types of the homogeneous broadening at different vibrational levels. The appearance of additional lines in the CARS spectrum due to mixing of high-lying vibrational levels by Fermi coupling was considered numerically in the frame of a simple model. A comparison of calculated and experimental spectra has been made.     

超快非均质电子转移的优化控制研究(Ⅰ)

本文用三能级的单振动模型,模拟了从二萘嵌苯到TiO2超快电子转移的动力学过程,发现在弱电子转移耦合下,电子在激光场的作用下激发至分子激发态转移然后到半导体导带,在强电子转移耦合下,电子直接由基态转移到半导体导带。在优化控制的理论模拟中以电子激发态的振动基态为目标态,考虑了不同注入位置条件下的电子转移的动力学过程,研究了优化激光场在给定时间内实现目标态的过程,由于从分子激发态到半导体的超快电子转移,只有当分子激发态能级与半导体导带底能级简并时,才能实现较高的目标态产生率。     

Relaxation Dynamics In Photo-Excited Halogen-Bridged Pt-Complexes Studied By Femtosecond Luminescence Spectroscopy

The ultrafast dynamics of excited electronic states in a series of quasi-one-dimensional halogen-bridged platinum-complexes was investigated by using femtosecond luminescence spectroscopy. In Pt-Br system, the wave-packet oscillation of the local vibration of self-trapped excitons (STEs) was observed. The time evolutions of luminescence intensity in Pt-Br and Pt-Cl were successfully described by using a model based on a wave-packet motion on the interaction mode coordinate. In Pt-I, very fast decay was observed, suggesting the existence of efficient non-radiative decay channel directing to structural change.     

Microwave spectrum of chloromethyl methyl ether

The microwave spectrum of chloromethyl methyl ether has been studied in the region 12.4–40 GHz. For ³⁵Cl species, a- and c-type transitions have been assigned for the ground state, the first excited state of the chloromethyl torsional mode, and the first excited state of the methyl torsional mode. Assignments were also made for the ground state of ³⁷Cl species. The assigned transitions are due to the gauche conformer. The nuclear quadrupole coupling constants were determined for the ground state of ³⁵Cl and ³⁷Cl species. The observed A-E splittings of the rotational transitions arising from the three vibrational states indicate a strong coupling between the two torsional vibrations. A model calculation based on the Hamiltonian previously used by Butcher and Wilson (J. Chem. Phys.40, 1671 (1964)), was carried out to account for the splittings and the vibrational frequencies of the two torsional modes. The barrier to internal rotation of the methyl group is estimated to be V₃ = 647 ± 17 cm^?1 (1.84 ± 0.05 kcal/mole).     

Resonant interaction between localized and extended vibrational modes in Si: 18O under pressure

The interaction between localized and extended vibrational modes in solids is of central importance in understanding how local vibrational modes decay into phonons. Interstitial oxygen (O(i)) in silicon is a model system for studying such interactions. Using hydrostatic pressure, we have brought the antisymmetric stretch mode of (18)O(i) in silicon into resonance with the second harmonic of the (18)O(i) resonant mode. Infrared spectroscopy was used to observe an anticrossing between these two vibrational modes at pressures near 4 GPa. A model of the interaction between these modes produced excellent agreement with the experimentally observed frequencies and linewidths.     

Persistence of rotational bands in a coupled SU(3) model

To understand better the emergence of rotational structures in a variety of situations, a model in which two SU(3) irreps are coupled via a quadrupole-quadrupole (Q·Q) interaction is considered. Strong coupling of different SU(3) irreps gives rise to low-lying rotor bands. We study the excited bands that occur and the perturbation effects of the rotational decoupling. Persistence of rotational-like bands for a large range of coupling strengths is observed. However, although for very weak interaction strengths the electromagnetic transition rates are consistent with those of the rotor model, the excitation energy ratios look more vibrational, a phenomenon which has been observed in many nuclei.     

外场对分子纳米结电流-电压特性的影响

针对由金属电极/分子/金属电极组成的分子纳米结,应用扩展主方程的方法,考虑分子纳米结中影响其传输过程的外场、分子内的弛豫过程等因素研究了在外场作用下分子纳米结内的稳定电流和瞬间电流.由于分子内较强的电子-振动耦合,分子纳米结中的电流-电压曲线呈现台阶式非弹性特征.在不同的高斯型脉冲的激发作用下,分子纳米结中电流需要达到稳定的时间也不相同,脉冲宽度在1ps时瞬间电流现象明显,这时分子处于非平衡分布,分子两端的电流存在较大差异.随着脉冲宽度和外场偏压的增加,分子两端的电流趋于平衡.     

Analysis of electronic-vibrational spectra of uracil,thymine, and cytosine

A theoretical analysis of absorption spectra of uracil, thymine, and cytosine—nucleic acid bases— is carried out. Structural dynamic models of these molecules in their electronically excited states are constructed. On the basis of the calculated vibrational structure of the electronic spectra, different tautomeric forms of these molecules are determined. The possibility of modeling the influence of hydrogen bonds on the electronic-vibrational spectra is shown.     

飞秒激光控制的分子量子动力学研究：(Ⅰ)三维二能级系统

结合MCDTDH方法和优化控制理论，以吡嗪分子为例，模拟了在给定不同的目标态下具有3个振动模两个电子态的分子系统的量子动力学过程. 以电子激发态作为目标态，优化激光场为一个楔形脉冲，它所激发的电子波函数在两个调制模空间中振荡最后达到平衡位置，并有较高的目标态产生率.发现目标态的选择强烈地影响波函数随时间的演变情况，若目标态在各个模的平衡位置，在优化激光场的作用下，电子波函数被直接激发到其平衡位置；若目标态不在振动模的平衡位形，其电子波函数经过强烈的振荡以达到平衡态. 关键词： 优化控制 MCTDH 方法 分子量子动力学     

Excited state proton transfer and internal conversion in o-hydroxybenzaldehyde: new insights from non-adiabatic ab initio molecular dynamics

A recently developed non-adiabatic ab initio molecular dynamics method coupling the S₁ excited electronic state to the ground state by a surface hopping technique has been applied to study photoexcited o-hydroxybenzaldehyde. Vertical excitation of the enol tautomer to the π π* state leads to spontaneous proton transfer (PT) and thus formation of the keto tautomer. The PT process has been found to be entirely driven by the breathing mode of the H-chelate ring. In fact, there exists no barrier for PT in the S₁ state. Non-radiative decay of the π π* excited keto tautomer through internal conversion (IC) is observed on a picosecond time scale. The probability for a non-adiabatic surface hop from the S₁ state back to the ground state is seen to be correlated to the chelate ring breathing mode and to the temporal changes in the methoxy OH bond length. There are indications of an increased IC rate associated with the initial PT event.     

The Rotational Spectrum of OCCCS Revisited

The rotational spectrum of the linear chain molecule tricarbon oxide sulfide, OCCCS, was recorded at room temperature between 118 and 179 GHz using a new commercial millimeter-wave spectrometer. The observed transitions were analyzed together with hitherto unassigned transitions from measurements between 78 and 118 GHz. About 1900 rotational transitions of OCCCS in the vibrational ground state and in 13 excited bending states could be assigned, the latter including the eighth, ninth, and tenth excited state of the low-lying bending mode nu(7) as well as the second excited state of the bending mode nu(6). Besides the determination of effective constants for these newly identified vibrational states, our data also served to considerably improve the effective constants for some of the bending states already characterized in previous publications. Copyright 2000 Academic Press.     

Models of the Dynamics of Spatially Separated Broadband Electromagnetic Fields Interacting with Resonant Atoms

The Markov model of spontaneous emission of an atom localized in a spatial region with a broadband electromagnetic field with zero photon density is considered in the conditions of coupling of the electromagnetic field with the broadband field of a neighboring space. The evolution operator of the system and the kinetic equation for the atom are obtained. It is shown that the field coupling constant affects the rate of spontaneous emission of the atom, but is not manifested in the atomic frequency shift. The analytic expression for the radiative decay constant for the atom is found to be analogous in a certain sense to the expression for the decay constant for a singly excited localized ensemble of identical atoms in the conditions when the effect of stabilization of its excited state by the Stark interaction with the vacuum broadband electromagnetic field is manifested. The model is formulated based on quantum stochastic differential equations of the non- Wiener type and the generalized algebra of the Ito differential of quantum random processes.     

A role of solvent in vibrational energy relaxation of metalloporphyrins

The formation of a vibrationally excited photoproduct of metalloporphyrins upon (π, π*) excitation and its subsequent vibrational energy relaxation were monitored by picosecond time-resolved resonance Raman spectroscopy. Stokes Raman bands due to a photoproduct of nickel octaethylporphyrin (NiOEP) instantaneously appeared upon the photoexcitation. Their intensities decayed with a time constant of 300 ps, which indicates electronic relaxation from the (d, d) excited state (B_1g) to the ground state (A_1g), being consistent with the results of transient absorption measurements by Holten and coworkers. Anti-Stokes ν₄ and ν₇ bands for vibrationally excited (d, d) state of NiOEP decayed with time constants of 10 and 300 ps. The former is ascribed to vibrational relaxation, while the latter corresponds to the electronic relaxation from the (d, d) excited state to the electronic ground state. While the rise of anti-Stokes ν₄ intensity was instrument-limited, the rise of anti-Stokes ν₇ intensity was delayed by 2.6±0.5 ps, which indicates that intramolecular vibrational energy redistribution has not been completed in subpicosecond time regime. To study a mechanism of intermolecular energy transfer, solvent dependence of the time constants of anti-Stokes kinetics was investigated using various solvents. No significant solvent dependence of the rise and decay constants was observed for NiOEP. For an iron porphyrin, we observed two phases in intermolecular energy transfer. The fast phase was insensitive to solvent and the slow phase depended on solvents. A model of classical thermal diffusion qualitatively reproduced this behavior. For solute-solvent energy transfer process, low-frequency modes of proteins seem to be less important.     

On the effect of phonon decay on electronic transitions in ionic crystal semiconductors

Generally electronic processes in semiconductors are accompanied by phonon excitations. These excitations themselves influence electronic transitions. On the other hand excited phonons decay by interaction with other impurities in the crystal, which act as a heat-bath. The resulting competition between phonon exciting electronic processes and phonon decay is described by Pauli's master equation. By expansion of its solutions into phonon decay solutions the problem can be separated into different decay equations for phonons and electrons as proposed by Stumpf. Assuming linear phonon-heat-bath coupling the phonon decay equation can be solved exactly by a generating function technique. The appropriate phonon decay frequencies are calculated for a simple heat-bath model.     

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.