Excited-state relaxation of Ag8 clusters embedded in helium droplets

Neutral silver clusters Ag(N) are grown in ultracold helium nanodroplets. By exploiting a strong absorption resonance recently found for Ag8, first photoelectron spectra of this neutral species are recorded. Variation of the laser photon energy reveals that direct vertical two-photon ionization is hindered by rapid relaxation into the lower edge of a long-living excited state manifold. The analysis of the dynamics gives a precise value of (6.89+/-0.09) eV for the vertical ionization potential of Ag8. The influence of the helium matrix on photoemission is discussed.     

Experimental dependence of two-photon absorption efficiency on statistical properties of laser light

The fluorescence intensity excited by two-photon absorption of the 514.5 nm argon laser line has been investigated for various oxasol derivatives. The fluorescence intensity was dependent on the statistical properties of the 514.5 nm argon laser line and was a factor 1.52-1.86 larger for absorption of a multifrequency laser line than in the case of a single frequency laser line.     

A pseudopotential study of molecular spectroscopy in rare gas matrices: absorption of NO in argon

We present a pseudopotential method to study the absorption spectroscopy of NO in an argon matrix modeled by a large albeit finite cluster. The excited states of NO are described with the virtual orbitals of a NO⁺ Hartree-Fock calculation plus a core-polarization operator to account for the electron-NO⁺ correlation. The argon atoms of the matrix are replaced by pseudopotentials for the repulsive contributions and core-polarization operators to account for matrix polarization and correlation with the excited electron. The model is shown to account for the matrix-induced transition shifts and also for the cut-off of the Rydberg series for n >3 reported in absorption experiments from the ground state. Received: 6 March 1998 / Revised: 1st June 1998 / Accepted: 16 June 1998     

Collisional transfer of rotational energy in the 2B1 electronic state of nitrogen dioxide

Collisional satellite lines have been observed in fluorescence from nitrogen dioxide excited by the 4545-Å line of the argon laser. The 13_0,13 level of the (0, 8, 0) vibrational state is populated by the laser and undergoes collisionally induced transitions to the 11_0,11, 15_0,15, and 17_0,17 states. These collisionally populated states are identified by their fluorescence to the well-studied (0, 0, 0) and (0, 1, 0) levels of the ground electronic state. These satellite lines are also observed in fluorescence to the (0, 2, 0) and (0, 3, 0) vibrational levels of the ground electronic state. The wavenumbers of those lines, together with those from unrelaxed fluorescence and previously published microwave transitions, allow vibrational and rotational constants for the higher vibrational states to be determined more accurately than was previously possible. Several much weaker forbidden transitions have also been observed, including ΔK_a = 0 through ?6 transitions in the (0, 8, 0)-(0, 0, 1) band.     

发射光谱研究氩气/空气混合气体介质阻挡放电能量传递过程

使用水电极介质阻挡放电装置,对比氩气与氩气/少量空气的混合气体以及空气与空气/少量氩气的混合气体放电的发射光谱,研究了氩气与空气相混合时气体放电中的能量传递过程。实验发现, 当氩气中加入少量的空气时,氩原子谱线均变弱,说明空气中的氮分子对氩原子的各激发态具有猝灭作用。并且随着空气含量的增加,各谱线变弱的速率不同。越是与氮分子的激发电位接近的氩原子的激发态被猝灭的作用越明显。另一方面,当空气中加入少量氩气时,发现氮分子第二正带系和氮分子离子第一负带系的谱线均被增强。说明在空气/少量氩气放电中,氮分子的激发由于亚稳态氩原子的潘宁激发传能而增强。因此在氩气/空气混合气体放电中,气体成分及比例影响放电的发光特性和能量传输特性。     

一种新型酰腙配体及其Sn配合物的荧光特性研究

用稳态荧光和时间分辨荧光研究了一种新型酰腙配体2-羟基甲醛-5-氯水杨酰腙(H3L)及Sn配合物(n-Bu2)Sn(HL)晶体、溶液和旋涂膜的光谱特性与分子结构的关系。实验结果表明,对H3L而言,与其稀溶液相比,晶体及旋涂膜的荧光强度依次增强,荧光峰位都有所红移,荧光寿命有所延长,其单分子跃迁能为240.2kJ.mol-1;对[(n-Bu2)Sn(HL)]而言,其晶体稳态荧光强度比在溶液中强且荧光峰位红移,旋涂膜产生了荧光猝灭,单分子跃迁能为230.4kJ.mol-1;与H3L相比较,(n-Bu2)Sn(HL)晶体的荧光强度要强接近4倍,荧光寿命变长。这些现象的物理机制是分子的共轭体系越大、分子的刚性越大其荧光强度越强,荧光寿命越长。     

Radiative relaxation in 2p-excited argon clusters

The emission of ultraviolet fluorescence radiation from variable size argon clusters is investigated with high spectral resolution in the Ar 2p-excitation regime. The fluorescence excitation spectra reveal strong fluorescence intensity in the Ar 2p-continuum, but no evidence for the occurrence of discrete low-lying core-exciton states in the near-edge regime. This finding is different from the absorption and photoionization cross section of argon clusters and the solid. The dispersed fluorescence shows a broad molecular band centered near 280 nm. The present work indicates that double and triple ionization via the LMM-Auger decay are required to initiate the fluorescence processes in the Ar 2p-continuum. The present results are consistent with the formation of singly charged, excited moieties within the clusters, which are assigned as sources of the radiative emission in the 280 nm regime. A fast energy transfer process (interatomic Coulombic decay (ICD)), which has been proposed by recent theoretical work, is assigned to be primarily the origin of these singly charged, excited cations besides intra-cluster electron impact ionization by the Auger electrons. Our findings give first possible experimental evidence for ICD in the core level regime.     

Spectral investigations on 2,3-bis(chloromethyl)-1,4- anthraquinone: solvent effects and host–guest interactions

Solvent effects on 2,3-bis(chloromethyl)-1,4-anthraquinone (DCMAQ) and the molecular recognition of DCMAQ in calix[8]arene were investigated using optical absorption and fluorescence emission techniques. Optical absorption spectra show n→π^* band in 350–500 nm region. It also indicates that the dipole–dipole interaction and solvent reorganization energies are responsible for the observed features in different solvents. The observed quantum yield of DCMAQ in different solvents is due to the formation of intermolecular hydrogen bond and reorientation of solvent molecule in the excited state of DCMAQ. Excited state dipole moment of DCMAQ is calculated by solvatochromic data and it shows a higher excited state dipole moment than ground state dipole moment. Optical absorption and fluorescence studies of DCMAQ in calix[8]arene elucidate the evidence for the formation of complex between DCMAQ and calix[8]arene. The inclusion ratios and inclusion constant of the host–guest complexes are also determined.     

碳碳双键共轭分子在玻璃态形成一个新的体积保守的扭转辐射态

采用时间分辨的单光子计数技术和TDDFT计算方法研究了激发态HY103分子的特性. 在室温下溶液中HY103分子被光激发后会发生光诱导的沿双键旋转的异构化,导致了HY103分子非常短的荧光辐射寿命和较弱的荧光辐射强度. 当HY103分子在77 K的玻璃态被光激发后,HY103分子的正常荧光辐射寿命被延长至2 ns左右,而且荧光辐射的强度也得到增强. 此外还观察到了一个新的辐射态和具有的性质. 这不仅能够诱导碳碳双键的共轭分子在空间束缚的环境中发生光致异构化,也可以形成一个新的稳定的辐射态.     

Fluorescence Enhancement of a Polymer Planar Waveguide Doped with Rhodamine B and Ag Nanoparticles

Planar polymer multi-model waveguides doped with Ag nano-particles and rhodamine B are fabricated and investigated by the spectroscopy analysis method as well as the M-line method. Experimental results shown that fluorescence enhancement occurs when excited by a wide band wavelength with Ag nano-particle concentration at a certain level. The maximum enhancement factor in our experiment is obtained to be about 3.8 when excited by 350 nm. Our study may have potential applications in polymers optical elements, such as polymer waveguide lasers and amplifiers.     

The ultraviolet spectrum of SO2 in matrix isolation and the vibrational structure of the 2348 Å system

The absorption spectra of SO₂ in solid neon and argon have been observed in the spectral regions near 2200 Å and 2900 Å. The spectral shifts of the electronic transitions in the matrix relative to the vapor are reported, including a shift with aging of the matrix. Implications for the interpretation of the vibrational structure of the 2348 Å system are discussed. A large spectral shift is attributed to a shift of the vibrational frequency 2ν₃′ of the excited electronic state.     

胭脂红分子结构的量子化学计算及荧光光谱机理研究

运用Gaussian 09W量子化学程序包,对胭脂红分子进行基态和激发态几何结构构型优化,计算得到激发态电子结构、分子前线轨道和发射光谱等信息;应用英国Edinburgh FLS920P 光谱仪,实验测定胭脂红溶液的荧光光谱。比较荧光发射光谱的计算值与实验值,吻合较好,说明优化所得构型基本合理。进一步对比胭脂红分子基态和激发态结构,分析荧光光谱产生的机理,发现胭脂红分子激发态几乎呈平面结构,为强荧光物质,其荧光由139→137轨道的跃迁产生。     

VUV excitation of benzene : C6H6 and C6D6 fluorescence and phosphorescence in argon and nitrogen matrices

Benzene isolated in argon or nitrogen matrix at about 5 K has been irradiated with photons of 6 eV (206.2 nm), 8.4 eV (147 nm), and 10 eV (123.6 nm) energy. In every case phosphorescence and fluorescence have been observed from the vibrationally relaxed states. The phosphorescence emission is still observed after the extinction of the excitation during the warming up as a thermoluminescence. The phosphorescence versus fluorescence ratio increases when passing from a nitrogen matrix to an argon matrix and as the photon energy increases. The main conclusion is that, in the condensed phase, the electronic relaxation processes leading to the emitting states are not as fast as usually assumed.     

Resonance fluorescence of gaseous chlorine excited with a single longitudinal mode argon ion laser

Resonance fluorescence spectra of gaseous chlorine, excited with a high power single longitudinal mode argon ion laser which was tuned through the lasing profiles of the 4880-, 4965-, 5017-, and 5145-Å lines, were studied. Five progressions of fluorescence lines were found and assigned as the fluorescence of ³⁵Cl³⁵Cl and ³⁷Cl³⁷Cl isotopic molecules resonantly excited from v = 0 and 1 levels of the X¹Σ state to the B³Π state. The fluorescence line positions agreed with those of the theoretical calculation within 0.2 cm^?1. The fluorescence intensities were very weak due to the extremely small transition probability between the B³Π and the X¹Σ states.     

The laser-induced fluorescence spectrum of the 1,2,3-trifluorobenzene radical cation

Laser-induced fluorescence spectra of the radical cation of 1,2,3-trifluorobenzene have determined the origin of the electronic transition and the lifetime of the excited state in both the gas phase and solid Ne matrices. The gas phase spectrum shows relatively poorly resolved vibrational structure, as the lines seem to be badly broadened by rotational contours. The matrix spectra show extensive, well-resolved vibrational structure with small but noticeable matrix perturbations. The structure is also rather irregular and differs considerably between the ground and excited states. All of these observations are consistent with a considerable change in geometry between the two electronic states.     

取代效应对脂滴检测NAPBr染料分子的双光子吸收和激发态性质影响的理论探究

双光子荧光染料分子在生物医学成像中具有广阔的应用前景,但取代效应对分子结构以及光物理性质影响的探求相对匮乏. 本文设计并研究了一系列脂滴检测染料分子,分析了分子的光学性质以及无辐射跃迁等. 通过分子内弱相互作用和电子- 空穴布居分析,阐述了其内在机理. 结果表明,所研究的分子均具有优良的光物理性能、高效荧光量子产量、大的斯托克斯位移以及显著的双光子吸收截面等. 本工作合理地解释了实验现象并阐述了取代效应对脂滴检测NAPBr染料分子的双光子吸收和激发态性质的影响,这为设计新型的高效有机分子提供了理论指导.     

Isolated atoms,molecules and clusters

The basic constituents of matter, namely, atoms molecules and small clusters can be isolated in a solid rare-gas-matrix (RGM) and be characterized by Mössbauer Spectroscopy (MS). Experiments can be conducted both by the absorption method using a co-evaporation method of Mössbauer isotopes or by emission spectroscopy where source nuclei are isolated in the RGM. Experimental aspects of both techniques are outlined. Examples of applications of RGMI-MS are described, namely,⁵⁷Fe clustering with noble-metals (Cu, Ag, Au); unusual electronic states of Fe following⁵⁷Co e.c. decay; species formed by the bonding of Fe⁰, in its ground state, to small molecules are compared with those formed by Fe in its various excited states; and finally, the characterization of atomic I⁰ and Te⁰ and Te^?1 embedded in a solid argon matrix.     

（7—甲氧基—4—亚甲基）香豆素基—单氮杂18—冠—6的合成及其？…

合成、鉴定了题示光敏离子载体（ＭＭＣ－ＭＡＣ（Ｏ５）。其中不同ｐＨ值水溶液中吸收和荧光光谱的变化,计算得该剂基态和激发态分子的酸性常数（ｐＫａ＝８．８４,ｐＫａ＾＊＝５．１１）。基于在不同溶剂中荧光光谱的变化,由Ｓｏｌｖａｃｈｒｏｍｉｃ法,借助Ａｌｃｈｅｍｙ２０００量化计算软件,估算得该分子的基态和激发态偶极矩,分别为３．１１Ｄ和８．１３Ｄ。同时发现,ＭＭＣ－ＭＡＣ（Ｏ５）水溶液除氧后其荧光强度奇     

Energy pooling to the level arising from collisions between pairs of metastable atoms

The energy-pooling rate coefficient for the process has been measured. The barium atoms were excited by a cw diode laser tuned to the frequency of the 791.3 nm intercombination line and the metastable atoms in the 6s5d state were produced due to radiative and collisional depopulation of the laser-excited 6s6p state. The measurements were performed at number densities of about and at 30 mbar argon as the buffer gas. Most of the barium ground state atoms in the excitation zone were transferred to the trip let metastable state at the laser pump power applied. The energy pooling rate coefficient was determined by comparing the fluorescence intensity of the barium 553.6 nm resonance line and the fluorescence intensity of the intercombination line 791.3 nm. In addition, the populations of the metastable atoms were probed with low intensity laser radiation from a single mode ring dye laser. The rate coefficient was found to be at . Received: 11 April 1997 / Revised: 24 September 1997 / Accepted: 10 December 1997     

Solvent Effects on the Spectroscopic Properties of Styrylquinolinium Dyes Series

The study on the relationship between the structure and spectroscopic properties of styrylquinolinium dyes were carried out by measuring the electronic visible absorption, steady-state and time-resolved fluorescence spectra of quinoline based hemicyanine dyes. The influence of the solvent on absorption and emission spectra and the solvatochromic properties, observed for both ground and first excited states, for all the dyes were applied for the evaluation of their excited state dipole moments. The ground state dipole moments of dyes under the study were established by applying ab initio calculations. The measured, using solvatochromic methods, excited state dipole moments of tested hemicyanines are in the range from 5.38 to 18.90 D and the change in the dipole moments caused by excitation were found to differ from 1.88 to 6.64 D. It was observed that for all tested dyes the dipole moments of the excited states were higher than those of a ground states. The fluorescence lifetime measurements with picosecond resolution was performed for entire series of hemicyanine dyes possessing different dialkylamino groups attached to the phenyl ring. The average lifetimes of the dye fluorescence, determined from the measured data by multi-order exponential decay curve fitting, were in the range from about 120 to 1200 ps at the fluorescence peak wavelength. The fluorescence lifetime measurements were performed for dyes in ethyl acetate solutions. The time-resolved fluorescence spectra measurements allowed to propose the mechanism of the dyes excited states deactivation.