Anion Mass Spectrometry Study of Ion-Pair Photodissociation of CO2 in the XUV Energy 19.70-22.24eV

We demonstrate anion mass spectrometry using the Hefei synchrotron radiation source to investigate the ion-pair dissociation processes of molecules. The efficiency curve of the O^- anionic product via ion-pair dissociations of CO2 is recorded with tunable extreme vacuum ultraviolet photons （energy： 19.70-22.24 eV） and compared with the spectrum available in the literature. The possible dynamics of CO2 ＋ hv → CO^＋＋ O^- in this energy range is discussed.     

Erratum: Photodissociation Efficiency Spectroscopy Study of the Rydberg Excited Ion-Pair States of Carbon Dioxide

In our paper published on Chinese Physics Letters 26（2009）103401, there were some mistakes in Table 1. Here is the corrected table：     

Fast decay of high vibronic S1 states in gas-phase benzene

Lifetimes of different vibronic levels at high excess energies in the S₁ state of isolated benzene molecules are measured using for the first time a two-photon ionization pump–probe technique with UV femtosecond pulses. For the 6¹1³ state (3290 cm^-1 excess energy) at the onset of the ‘channel three’ a biexponential decay is found with a fast (τ_f=20 ps) and a slow (τ_s>500 ps) component. The values are in line with previous sub-Doppler high-resolution measurements of this band in our laboratory. We explain the measured faster decay (τ_f=900 fs, τ_s=100 ps) of the 7¹ state at a lower excess energy of 3077 cm^-1 by a simultaneous excitation of the adjacent 6¹ ₀1³ ₀16¹ ₁ hot band leading to a vibronic state of higher excess energy and faster decay. The vibronic levels 6¹1⁴ and 7¹1¹ at a higher excess energy of ≳4000 cm^-1 show a biexponential decay of τ_f=550 fs, τ_s=30 ps and τ_f≲300 fs, τ_s=20 ps, respectively. The experimental results point to dynamic processes within the vibronic level manifold of the S₁ state and a fast nonradiative electronic relaxation process. Received: 3 November 1999 / Published online: 5 July 2000     

Infrared-laser-pulse control of bond- and state-selective excitation, dissociation and space quantization: application to a three-dimensional model of HONO2 in the ground electronic state

Selective control over the vibrational excitation and space quantization of the dissociation fragments by optimally designed linearly polarized and shaped infrared (IR) laser pulses of the picosecond (ps) and subpicosecond duration is demonstrated by means of quantum-dynamical simulations within the Schr?dinger wave-function formalism for a three-dimensional (3-D) model of HONO₂ in the ground electronic state, wherein the OH and the ON single-bond stretches are explicitly treated, together with the bending angle between them, on the basis of the ab initio defined 3-D potential-energy surface and dipole function. The high-lying zeroth-order vibrational states of the OH bond are prepared selectively both below and above the dissociation threshold of the ON single bond, and demonstrate a quasi-periodic oscillatory behaviour, manifesting intramolecular vibrational energy redistribution (IVR) on the picosecond timescale. Selective breakage of the ON single bond in HONO₂ with more than 97% probability is demonstrated, along with control of the space quantization of the dissociation fragments: the OH fragments rotating clockwise, OH(c), and anticlockwise, OH(a), are prepared selectively, with the OH(a)/OH(c) branching ratio being as high as 10.975. The results obtained show that optimally designed strong and short IR-laser pulses can compete against IVR and manipulate vibrational excitation and dissociation of polyatomic molecules. Received: 3 November 1999 / Published online: 13 July 2000     

Resonant two-step photoionization of molecules: Effects of pulse sequence,pulse duration and delay time of two lasers on ionization probability and selectivity

Using rate equations the effect of different pulse sequences, pulse durations, and delay times of two lasers on ionization probability and selectivity in resonant two-step photoionization of molecules is investigated. The results demonstrate to what extent a given selectivity of the absorption or relaxation of the intermediate electronic, state is influenced by a special combination of these parameters.     

Unified theory of bound and scattering molecular Rydberg states as quantum maps

Using a representation of multichannel quantum defect theory in terms of a quantum Poincaré map for bound Rydberg molecules, we apply Jung's scattering map to derive a generalized quantum map, that includes the continuum. We show that this representation not only simplifies the understanding of the method, but moreover produces considerable numerical advantages. Finally we show under what circumstances the usual semi-classical approximations yield satisfactory results. In particular we see that singularities that cause problems in semi-classics are irrelevant to the quantum map.     

Self-action effects in ionization and fragmentation of toluene by femtosecond laser pulses

Occurrence and influence of several self-action effects, induced in the entrance window of a time-of-flight interaction chamber, on the ion and fragment yields of the toluene molecule in the focus of a Ti:sapphire laser pulse are analyzed. Experimental data are obtained using different focusing geometries and are compared with results from numerical simulations using a nonlinear pulse propagation model as well as those from the strong-field S-matrix theory. It is shown that (a) self-focusing leads to a displacement of the focus while amplified small perturbations of the input beam result in hot spots in the spatial distribution and in an energy-dependent focus area, (b) small self-phase modulation changes the form of the spectrum and broadens it slightly. A strong increase of the toluene fragmentation appears to correlate to linear and nonlinear changes in the focal spot area, while the scenario of excitation of Raman modes proposed in an earlier publication is ruled out as the dominant effect.This revised version was published online in March 2005. In the previous version, the published online date was missing     

Detection of NO traces Using resonantly enhanced multiphoton ionization: A method for monitoring atmospheric pollutants

Resonantly enhanced multiphoton ionization (REMPI) is proposed as an ultrasensitive detection method forreal-time monitoring of atmospheric pollutants in situ. The technique is demonstrated in the laboratory for NO diluted in pure nitrogen at 560 mbar. The MPI current resulting from (2+1) photon ionization of NO via the resonantC ² H (v=0) state has been measured for several NO concentrations. Detection levels as low as 50 ppt have been obtained.Laboratoire associé à l'Université de Paris-Sud     

Theory of Tunnel Ionization in Complex Systems

We present a detailed derivation of the Ammosov-Delone-Krainov theory of tunnel ionization in complex systems （CS-ADK）. A few mistakes in the previous works have been found and corrected. The theory is then applied to CO2, showing that CS-ADK yields better agreement with experiment than the molecular ADK theory.     

Photoelectron angular distributions of molecules in bichromatic laser fields of circular polarization

Photoelectron angular distributions (PADs) from above-threshold ionization of O₂ and N₂ molecules irradiated by a bichromatic laser field of circular polarization are studied. The bichromatic laser field is specially modulated such that it can be used to mimic a sequence of one-cycle laser pulses. The PADs are greatly affected by the molecular alignment, the symmetry of the initial electronic distribution, and the carrier-envelope phase of the laser pulses. Generally, the PADs do not show any symmetry, and become symmetric about an axis only when the symmetric axis of laser field coincides with the symmetric axis of molecules. This study shows that the few-cycle laser pulses can be used to steer the photoelectrons and perform the selective ionization of molecules.     

Theoretical Study of the Influence of Femtosecond Laser Wavelength on the Evolution of a Double-Minimum Electronic Excited State Wave Packet for NaRb

Employing the two-state model and the time-dependent wave packet method, the influence of femtosecond laser wavelength on the evolution of the double-minimum electronic excited state wave packet is numerically investigated. For different laser wavelengths, evolutions of the double-minimum electronic excited state wave packet with time and internuclear distance are different. One can control the evolution of the wave packet by varying the laser wavelength appropriately, which will benefit the light manipulation of atomic and molecular processes. Furthermore, study of the dynamics of the NaRb molecule may yield clues to creating an ultracold molecule.     

Study on Non-Sequential Double Ionization of Aligned Diatomic Molecules in Strong Laser Fields

We develop a semiclassical model to describe the non-sequential double ionization of aligned diatomic molecules in an intense linearly polarized field. It is found that in the tunnelling regime, the oriented molecule shows geometric effects on double ionization process when aligned parallel and perpendicular to the external field. Our results are qualitatively consistent with the recent experimental observations.     

激发态RbHe(Ar)分子的光离解

本文研究了Rb（5^2P) He(Ar) nhv→Rb(7^2D) He(Ar) n-1)hv过程，激光频率调离Rb7D5/2→5P3/2跃迁谱线20－100cm^-1，测量了精细结构普线强度分支出I（7D3／2→5P1／2）／I（7D5／2→5P3／2）。测量结果表明，原相互作用势和非绝热效应在分子离解动力学中起关键作用。     

Fabrication of large-scale ultra-smooth metal surfaces by a replica technique

The IR double-resonance techniques IR/R2PI (infrared/resonant 2-photon ionization), IR/PIRI (infrared-photo-induced Rydberg ionization) and IR-photodissociation spectroscopy are valuable tools to investigate structure, vibrations, and dynamical processes of neutral and ionic hydrogen-bonded clusters containing aromatic molecules. In this paper we report on the application of the IR double-resonance techniques to determine the NH and OH stretching vibrations of 4-aminophenol and 4-aminophenol(H₂O)₁, both in the neutral (S₀) and ionic (D₀) ground state. All vibrational frequencies obtained for 4-aminophenol and the cluster are compared with the values obtained from ab initio and DFT calculations. In the S₀ state, a trans-linear arrangement of 4-aminophenol(H₂O)₁ is obtained containing an O-H·· O hydrogen bond. In the D₀ state an overlay of two spectra can be observed resulting from the trans-linear structure and a second structure which contains a N-H·· O hydrogen bond. The observation of these two structures within the ion is an interesting example of a rearrangement reaction in the ionic state. Received: 3 November 2000 / Accepted: 6 November 2000 / Published online: 9 February 2001     

Influence of the photoionization process on the fragmentation of laser desorbed polycyclic aromatic hydrocarbons

Characterization of polycyclic aromatic hydrocarbons (PAHs) samples has been performed by laser desorption combined with multi-photon ionization technique using two different geometries of the ionization laser beam. This comparative study evidences the strong influence of ionization laser fluence on PAH fragmentation. Through a ∼10³ enlargement of the ionization probe volume and 10⁴ reduction of laser fluence over previous studies, fragment free mass spectra are obtained with higher sensitivity and selectivity. The ability to measure fragment free PAH mass spectra is a very important step in the end goal of measuring complex unknown mixtures of PAH desorbed from solid surface such as soot samples.     

Photodissociation dynamics of CF3I investigated by two-color femtosecond laser pulses

We report an experimental study of the multiphoton dissociation dynamics of CF₃I performed on a home-built femtosecond laser pump-probe system, with time-of-flight mass spectrometer. The first repulsive A band and the 5pπ³7sσ υ₂=1 Rydberg state of CF₃I were accessed by one- and two-photon transitions at 267 nm, respectively, with the latter two-photon absorption followed by a further two-photon probe transition at 401 nm to the state of the parent ion. The observed signals from the CF₃ ⁺ and I⁺ fragments show similar multi-component exponential decay patterns but the former is 4 times stronger than the latter. However, the parent CF₃I⁺ signal was observed to evolve in a very different manner, decreasing sharply when probed in the first 289 fs following excitation and subsequently rising again after 860 fs to a constant level below that measured at negative pump-probe delay times when the pump and probe pulses exchange roles. This dip observed in the parent ion profile, is very different from that previously reported at shorter pump wavelengths of 264 nm or 265 nm, and is interpreted as the competition between two different ionization channels. One from the vibrationally excited υ₂=1 of the irradiated Rydberg state and the other from the dissociative vibrational origin of the same electronic state which is populated by internal vibrational relaxation.     

Fragmentation of CO in Femtosecond Laser Fields

Fragmentation of CO in a linearly polarized femtosecond laser field within the intensity order of 10^14 W.cm^-2 at 820nm is investigated experimentally by using velocity mapping technique. According to the observed kinetic energy and angular distributions of different charged fragment ions, fragmentation channels of CO are proposed. The angular distributions provide helpful information for assigning the dissociation channels.     

锂分子里德堡态和双激发态的重新分类

根据里德堡轨道的类氢nλ特性 ,对 7Li2 实验已观测到的和理论计算给出的 6 8个电子态进行了分类 ,把这些态划分为核实贯穿里德堡态和核实非贯穿里德堡态 .讨论了双电子激发态和里德堡态的微扰 ,也讨论了这种分类的意义     

Laser-excited nonlinear properties of BaF2 and its application in a single-shot spatially insensitive autocorrelator

A detailed investigation of laser-generated nonlinear processes of undoped barium fluoride is presented including two-photon-excited exciton fluorescence, color-center formation and damage-threshold measurements. A single-shot autocorrelator based on two-photon fluorescence of BaF₂ was constructed to measure the phase and amplitude of pulses provided by large apeture excimer lasers. The capabilities of the autocorrelator are demonstrated at 248 nm and 268 nm with pulses in the regime of 100 fs to 10 ps.     

Structural Deformation of CO22+ in Intense Femtosecond Laser Fields

The angular distributions of CO^＋ from the dissociation of CO2^2＋ and CO2^＋ in intense femtosecond laser fields （45 fs, about 5 × 10^15 W/cm^2） are studied at a laser wavelength of 800nm based on the time-of-flight mass spectra of CO^＋ fragment ions. The experimental results show that structural deformation occurs in the charge state of CO2^2＋ and the CO^＋ maintains linear geometrical structure.