Predissociation Dynamics of B State of Methyl Iodide with Femtosecond Pump-probe Technique

The predissociation dynamics of B Rydberg state of methyl iodide is studied with femtosecond two-color pump-probe time-of-°ight spectra at pump pulse of 400 nm and probe pulse of 800 nm. The dominant product channels are the CH3I+ and CH3+ formation. The time-dependent signals for CH3I+ and CH3+ ions are obtained. Both of the signal curves can be ˉtted by biexponential decays with time constants of ?1 and ?2, ?1 is assigned to the lifetimes of high Rydberg states, which can be accessed by absorbing three 400 nm pump pulses and ?2 re°ects the dynamics of B Rydberg state, which is accessed with two pump pulses. The lifetime of B Rydberg state is determined to be about 1.57 ps, which is incredibly consistent with the previous studies. The results were interpreted as a multiphoton dissociative ionization processes.     

Photodissociation of CS2+( 2 Πg) via (1+1) Excitation

Photodissociation dynamics of CS2+molecular ions has been investigated by (1+two-photon resonance technique. CS2+were prepared by (3+1) resonance-enhanced multi-photon ionization (REMPI) of CS2molecules at 483. 2nm. The photofragment S+excitati (PHOFEX) spectra were recorded by scanning another laser in the 424~482nm region, and we assigned essentially to CS2+(~A2Πu,3/2(v′=0~4)←~X2Πg,3/2(0,0,0)) and (~A2Πu,1/2(v′=0,4)←~X2Πg,1/2(0,0,0)) (herev′=v1′+(1/2)v2′) transitions. The S+production channel wpreliminarily attributed to, (i) one-photon excitation CS2+from the ground state~X2Πgto texcited state~A2Πu; (ii) vibronic coupling between the~A2Πustate and the high vibrational lev in the~X2Πgstate; (iii) second photon excitation from the coupling vibrational levels to the excied state~B2Σu+and dissociation to produce S++ CS via the repulsive4Σ-state through spin-orb interaction between the~B2Σu+and4Σ-states.     

Wave packet calculations on the effect of the femtosecond pulse width in the time-resolved photodissociation of CH3I in the A-band

The effect of changing the temporal width of the pump and probe pulses in the time-resolved photodissociation of CH(3)I in the A-band has been investigated using multisurface nonadiabatic wave packet calculations. The effect is analyzed by examining properties like the photodissociation reaction times and the CH(3) fragment vibrational and rotational distributions, by using four different widths of the pump and probe pulses, namely pulses with full-width-at-half-maximum of 100, 50, 20, and 10 fs. Simulations are carried out for two different excitation wavelengths, 295 and 230 nm, located to the red and to the blue of the maximum of the absorption spectrum, in order to explore possible effects of the excitation wavelength. The reaction times are found to decrease significantly with decreasing pulse temporal width. The times associated with the CH(3) + I*((2)P(1/2)) dissociation channels decrease more remarkably than those of the CH(3) + I((2)P(3/2)) channels. The results indicate that for excitation wavelengths located to the blue of the absorption spectrum maximum the effect of changing the pulse width is less pronounced than for wavelengths to the red of the spectrum maximum. On the contrary, the CH(3) vibrational and rotational distributions show little variation upon large changes in the pulse width. The trends found are explained in terms of the changes in the spectral bandwidth of the pulses and of the shape and slope of the absorption spectrum at the different excitation wavelengths.     

CS2 +多光子光解产生CS+的动力学研究

The dynamics on the multi-photon dissociation of CS2+ molecular ions to produce CS + ions has been investigated by measuring the CS + photofragment excitation（PHOFEX）spectrum in the wavelength range of 385～435 nm,where the CS2+ molecular ions were prepared purely by［3+1］multiphoton ionization of the neutral CS2molecules at 483.2 nm. With the ～60 ns delay,which is much more than the laser pulse width（～5 ns）,between ionization laser and dissociation laser,the threshold wavelength of dissociation laser to produce CS+ fragment ion from CS2+ molecular ions was obviously observed in the PHOFEX spectrum. The adiabatic appearance potential of the CS+ was determined to be（5.852 ± 0.005）eV above the X 2Σg,3/2（0,0,0）level of CS2+. The product branching ratios,（CS+/S+）,as measured from the PHOFEX spectra,increase from 0 to slightly larger than 1 in the wavenumber range of 47200～50400 cm-1 . The［1+1］dissociation mechanism to get to CS++S from CS2+ was discussed and preliminarily attributed to（i）CS2+（X 2Πg）→ CS2+（A2Πu）through one-photon excitation,（ii）CS2+（A2Πu）→ CS2+（X*）via internal conversion process due to the vibronic coupling between the A and X states,（iii）CS2+（X*）→ CS2+（B 2Σ+u）through the second photon excitation,and（iv）CS2+（B 2Σ+u）→CS +（X 2Σ+）+S（3P）,because of the potential curve crossing with the repulsive 4Σ- state and/or the 2Σ- state correlated with the second dissociation limit. However,when the dissociation laser overlaps the ionization laser in time scale in the laser-molecule interaction zone,the appearance threshold is not available in the PHOFEX spectrum. This fact shows that there are other mixed three-photon paths of［1+1+1'］,［1+1'+1'］,and［1+1'+1］to produce CS+ fragment ion from CS2+ molecular ions besides the above［1+1］dissociation mechanism,that is,CS2+（X 2Πg）→ CS2+（A 2Πu）through one-photon excitation［1］of dissociation laser,CS2+（A 2Πu）→CS2+（X*）via internal conversion process due to the vibronic coupling between the A and X states,CS2+（X*）→ CS2+（B 2Σ +u）through the second photon excitation by dissociation laser［1］or ionization laser［1'］,and third photon excitation by ionization laser［1'］or dissociation laser［1］to reach the adiabatic appearance potential to produce CS+ with the dissociation laser wavelengths longer than 423. 89 nm,at which the［1+1］dissociation mechanism to get to CS+ is unavailable.     

超声射流下12C16O+离子A2∏1/2,3/2←X2∑+激光诱导荧光激发谱

用一束波长为230.1 nm的激光, 通过(2+1)共振增强多光子电离(REMPI)过程激发超声射流冷却的CO分子制备处于基电子态X2∑+的CO+离子, 随后引入另一束可调谐激光将CO+离子激发至A2∏1/2,3/2态, 利用光电倍增管(PMT)检测发射的荧光信号强度随激发光波长的变化, 分别在487-493 nm和453-459 nm波长范围内获得了CO+离子A2∏1/2,3/2←X2∑+电子态跃迁(0,0)和(1,0)带的激光诱导荧光(LIF)激发谱.     

Stark-assisted population control of coherent CS(2) 4f and 5p Rydberg wave packets studied by femtosecond time-resolved photoelectron spectroscopy

A two-color (3+1(')) pump-probe scheme is employed to investigate Rydberg wave packet dynamics in carbon disulfide (CS(2) (*)). The state superpositions are created within the 4f and 5p Rydberg manifolds by three photons of the 400 nm pump pulse, and their temporal evolution is monitored with femtosecond time-resolved photoelectron spectroscopy using an 800 nm ionizing probe pulse. The coherent behavior of the non-stationary superpositions are observed through wavepacket revivals upon ionization to either the upper (12) or lower (32) spin-orbit components of CS(2) (+). The results show clearly that the composition of the wavepacket can be efficiently controlled by the power density of the excitation pulse over a range from 500 GWcm(2) to 10 TWcm(2). The results are consistent with the anticipated ac-Stark shift for 400 nm light and demonstrate an effective method for population control in molecular systems. Moreover, it is shown that Rydberg wavepackets can be formed in CS(2) with excitation power densities up to 10 TWcm(2) without significant fragmentation. The exponential 1e population decay (T(1)) of specific excited Rydberg states are recovered by analysis of the coherent part of the signal. The dissociation lifetimes of these states are typically 1.5 ps. However, a region exhibiting a more rapid decay ( approximately 800 fs) is observed for states residing in the energy range of 74 450-74 550 cm(-1), suggestive of an enhanced surface crossing in this region.     

Ultrafast S1 to S0 internal conversion dynamics for dimethylnitramine through a conical intersection

Electronically nonadiabatic processes such as ultrafast internal conversion (IC) from an upper electronic state (S(1)) to the ground electronic state (S(0)) though a conical intersection (CI), can play an essential role in the initial steps of the decomposition of energetic materials. Such nonradiative processes following electronic excitation can quench emission and store the excitation energy in the vibrational degrees of freedom of the ground electronic state. This excess vibrational energy in the ground electronic state can dissociate most of the chemical bonds of the molecule and can generate stable, small molecule products. The present study determines ultrafast IC dynamics of a model nitramine energetic material, dimethylnitramine (DMNA). Femtosecond (fs) pump-probe spectroscopy, for which a pump pulse at 271 nm and a probe pulse at 405.6 nm are used, is employed to elucidate the IC dynamics of this molecule from its S(1) excited state. A very short lifetime of the S(1) excited state (～50 ± 16 fs) is determined for DMNA. Complete active space self-consistent field (CASSCF) calculations show that an (S(1)/S(0))(CI) CI is responsible for this ultrafast decay from S(1) to S(0). This decay occurs through a reaction coordinate involving an out-of-plane bending mode of the DMNA NO(2) moiety. The 271 nm excitation of DMNA is not sufficient to dissociate the molecule on the S(1) potential energy surface (PES) through an adiabatic NO(2) elimination pathway.     

Femtosecond time-resolved photoelectron-photoion coincidence imaging of multiphoton multichannel photodynamics in NO2

The multiphoton multichannel photodynamics of NO(2) has been studied using femtosecond time-resolved coincidence imaging. A novel photoelectron-photoion coincidence imaging machine was developed at the laboratory in Amsterdam employing velocity map imaging and "slow" charged particle extraction using additional electron and ion optics. The NO(2) photodynamics was studied using a two color pump-probe scheme with femtosecond pulses at 400 and 266 nm. The multiphoton excitation produces both NO(2) (+) parent ions and NO(+) fragment ions. Here we mainly present the time dependent photoelectron images in coincidence with NO(2) (+) or NO(+) and the (NO(+),e) photoelectron versus fragment ion kinetic energy correlations. The coincidence photoelectron spectra and the correlated energy distributions make it possible to assign the different dissociation pathways involved. Nonadiabatic dynamics between the ground state and the A (2)B(2) state after absorption of a 400 nm photon is reflected in the transient photoelectron spectrum of the NO(2) (+) parent ion. Furthermore, Rydberg states are believed to be used as "stepping" states responsible for the rather narrow and well-separated photoelectron spectra in the NO(2) (+) parent ion. Slow statistical and fast direct fragmentation of NO(2) (+) after prompt photoelectron ejection is observed leading to formation of NO(+)+O. Fragmentation from both the ground state and the electronically excited a (3)B(2) and b (3)A(2) states of NO(2) (+) is observed. At short pump probe delay times, the dominant multiphoton pathway for NO(+) formation is a 3x400 nm+1x266 nm excitation. At long delay times (>500 fs) two multiphoton pathways are observed. The dominant pathway is a 1x400 nm+2x266 nm photon excitation giving rise to very slow electrons and ions. A second pathway is a 3x400 nm photon absorption to NO(2) Rydberg states followed by dissociation toward neutral electronically and vibrationally excited NO(A (2)Sigma,v=1) fragments, ionized by one 266 nm photon absorption. As is shown in the present study, even though the pump-probe transients are rather featureless the photoelectron-photoion coincidence images show a complex time varying dynamics in NO(2). We present the potential of our novel coincidence imaging machine to unravel in unprecedented detail the various competing pathways in femtosecond time-resolved multichannel multiphoton dynamics of molecules.     

Control of bond-cleaving reactions of free protonated tryptophan ion by femtosecond laser pulses

The excited-state dynamics of protonated tryptophan ions is investigated by photoinduced fragmentation in the gas phase. In contrast to the neutral molecule that decays on the nanosecond time scale, the protonated species exhibits an ultrafast decay with two time constants of about 400 fs and 15 ps. In addition, after UV excitation by a pump photon at 266 nm, specific photofragments, and in particular the NH3-loss channel, can be enhanced by the absorption of a probe photon at 800 nm. The bond-cleaving reactions can thus be controlled by a variation of the pump/probe delay.     

243～263nm CH3COCH3 的多光子电离研究

在243～263 nm紫外光波段通过质量选择光电离激发谱研究了丙酮（CH3COCH3）的光化学反应通道。分析母体离子CH3COCH3+和碎片离子CH3CO+ 、 CH3+的光电离激发谱和质谱峰宽可以知道: 此光波段丙酮分子的光化学反应主要包括了丙酮分子经由(S1,T1)中间态产生母体离子的（1+1）双光子电离通道,母体离子进一步解离产生碎片离子CH3+的“光电离-光解离”通道和丙酮分子经由(S1,T1)中间态解离成中性自由基碎片CH3CO后再进一步被双光子电离的“光解离-光电离”通道。由母体离子光电离激发谱双光子阈值波长（255.67 nm）给出的丙酮电离势（IP）为（9.696±0.004）eV。     

The photodissociation reaction dynamics of CF(3)I at 304 nm ((3)Q(0+), (1)Q(1)<--(3)Q(0+), and (3)Q(1))

The photodissociation of CF(3)I at 304 nm has been studied using long time-delayed core-sampling photofragment translational spectroscopy. Due to its capability of detecting the kinetic energy distribution of iodine fragments with high resolution, it is able to directly assign the vibrational state distribution of CF(3) fragments. The vibrational state distributions of CF(3) fragments in the I(*)((2)P(12)) channel, i.e., (3)Q(0+) state, have a propensity of the nu(2) (') umbrella mode with a maximum distribution at the vibrational ground state. For the I((2)P(32)) channel, i.e., (1)Q(1)<--(3)Q(0+), the excitation of the nu(2) (') umbrella mode accounts for the majority of the vibrational excitation of the CF(3) fragments. The 1 nu(1) (') (symmetric CF stretch) +nnu(2) (') combination modes, which are associated with the major progression of the nu(2) (') umbrella mode, are observed for the photodissociation of CF(3)I at the I channel, i.e., (3)Q(1) state. The bond dissociation energy of the CI bond of CF(3)I is determined to be D(0)(CF(3)-I)相似文献   

白光LED用黄色荧光粉Ba(Y1-0.5x-yAly)2S4:xHo3+的合成和发光特性

采用高温固相法合成了Ba(Y1-0.5x-yAly)2S4:xHo3+系列荧光粉。在465 nm蓝光激发下,荧光粉的发射光谱呈多谱带发射,主峰位于492、543和661 nm处,分别对应于Ho3+的5F3→5I8,(5S2,5F4)→5I8和5F5→5I8跃迁发射。研究了Ho3+和Al3+掺杂量对BaY2S4:Ho3+发光性能的影响。结果表明,随着Ho3+掺杂量的逐渐增大,荧光粉的发光颜色由绿色逐渐向红色转变;适量Al3+取代Y3+可以提高BaY2S4:Ho3+荧光粉的发光强度。荧光粉Ba(Y0.665Al0.3)2S4:0.07Ho3+在蓝光(465 nm)激发下发射黄光,是一种潜在的白光LED用黄色荧光粉。     

碘甲烷通过Ã态和C态的多光子电离

碘甲烷分子与激光相互作用,发生的光解、激发电离等化学或物理过程已由许多人进行过研究.本文报导用多光子电离飞行质谱和光电子能谱技术研究碘甲烷通过(?)态和(?)态的多光子过程的主要实验结果和结论.实验用Nd:YAG 激光器泵浦染料激光器,可调谐的染料(R590)激光经倍频或与YAG 基频1.06μm 混频后分别得到280nm 或366nm 附近的紫外光,能量为0.2—2mJ/脉冲,时间脉     

Vibrational dynamics of excited electronic states of molecular iodine

Femtosecond degenerate four-wave-mixing spectroscopy following an initial pump laser pulse was used to observe the wave packet dynamics in excited electronic states of gas phase iodine. The focus of the investigation was on the ion pair states belonging to the first tier dissociating into the two ions I-(1S) + I+(3P2). By a proper choice of the wavelengths of the initial pump and degenerate four-wave-mixing pulses, we were able to observe the vibrational dynamics of the B (3)Pi(u) (+) state of molecular iodine as well as the ion pair states accessible from there by a one-photon transition. The method proves to be a valuable tool for exploring higher lying states that cannot be directly accessed from the ground state due to selection rule exclusion or unfavorable Franck-Condon overlap.     

Photoinduced dissociation of electrospray-generated ions in an ion trap/time-of-flight mass spectrometer using a pulsed CO2 laser

An ion trap/time-of-flight (IT/TOF) mass spectrometer was developed and applied to infrared multiphoton dissociation (IRMPD) studies of ions generated by electrospray ionization. A pulsed 10.6- micro m laser beam from a CO(2) laser was used for excitation of trapped ions. Results from IRMPD of peptide ions show that this method provides useful information related to the amino acid sequence of analyzed peptides. Comparative studies show that IRMPD spectra are similar to those obtained using a 266-nm UV laser beam for excitation. However, in contrast to multiple-pulse excitation required at 266 nm, the energy of a single laser pulse in IRMPD is sufficient to induce dissociation of peptide ions. The laser power is practically an exclusive parameter that must be controlled in order to obtain IRMPD spectra that will provide the optimal structural information. It is further demonstrated that the IRMPD IT/TOF technique has the potential to probe the structural features of larger ions that cannot be readily fragmented by collision-induced dissociation (CID). A multiply charged ion of equine cytochrome c is successfully fragmented in a single laser pulse experiment. The IRMPD IT/TOF technique is also shown to be a promising tool for studying dissociation kinetics of peptide and protein ions. Unlike other methods that usually monitor the dissociation ion kinetics in a dissociation time frame of greater than milliseconds, the IT/TOF can promptly detect all product ions generated by the dissociation process, and thus monitor the dissociation process of peptides and proteins in a sub-millisecond time frame. This instrument allows us to determine the dissociation rates of cytochrome c ions using high-energy photoexcitation. It is found that the charge state of the protein ion has a significant effect on dissociation kinetics, which is consistent with that found under low-energy excitation experiments. It is shown that the increase in energy of a laser pulse from 130 to 180 mJ changes the dissociation rate constant for the +12 ion from k = 2.4 x 10(3) x s(-1) to k = 7.3 x 10(4) x s(-1). The +8 ion following excitation at 130 mJ dissociates slower with a rate constant of k = 2.6 x 10(2) x s(-1). The rate difference observed is attributed to conformational differences among the ions with different charge states.     

UV absorption cross sections between 230 and 350 nm and pressure dependence of the photolysis quantum yield at 308 nm of CF3CH2CHO

Ultraviolet (UV) absorption cross sections of CF(3)CH(2)CHO were determined between 230 and 350 nm by gas-phase UV spectroscopy. The forbidden n → π* transition was characterized as a function of temperature (269-323 K). In addition, the photochemical degradation of CF(3)CH(2)CHO was investigated at 308 nm. The possible photolysis channels are: CF(3)CH(2) + HCO , CF(3)CH(3) + CO , and CF(3)CH(2)CO + H . Photolysis quantum yields of CF(3)CH(2)CHO at 308 nm, Φ(λ=308nm), were measured as a function of pressure (25-760 Torr of synthetic air). The pressure dependence of Φ(λ=308nm) can be expressed as the following Stern-Volmer equation: 1/Φ(λ=308nm) = (4.65 ± 0.56) + (1.51 ± 0.04) × 10(-18) [M] ([M] in molecule cm(-3)). Using the absorption cross sections and the photolysis quantum yields reported here, the photolysis rate coefficient of this fluorinated aldehyde throughout the troposphere was estimated. This calculation shows that tropospheric photolysis of CF(3)CH(2)CHO is competitive with the removal initiated by OH radicals at low altitudes, but it can be the major degradation route at higher altitudes. Photodegradation products (CO, HC(O)OH, CF(3)CHO, CF(3)CH(2)OH, and F(2)CO) were identified and also quantified by Fourier transform infrared spectroscopy. CF(3)CH(2)C(O)OH was identified as an end-product as a result of the chemistry involving CF(3)CH(2)CO radicals formed in the OH + CF(3)CH(2)CHO reaction. In the presence of an OH-scavenger (cyclohexane), CF(3)CH(2)C(O)OH was not detected, indicating that channel (R1c) is negligible. Based on a proposed mechanism, our results provide strong evidences of the significant participation of the radical-forming channel (R1a).     

Spectral analysis of Mn2+, Co2+ and Ni2+: B2O3-ZnO-PbO glasses

This paper reports on the spectral properties of Mn2+, Co2+ and Ni2+ ions doped B2O3-ZnO-PbO glasses. XRD, FT-IR spectra and DSC profiles of these glasses have also been carried out, and the FT-IR profiles have shown the presence of both BO3 and BO4 units. It is interesting to notice that the FT-IR peak positions are slightly shifted towards higher energy with an increase in transition metal ion concentration change. From the measured DSC thermograms, glass transition (T(g)), crystallization (T(c)) and temperature of melting (T(m)) have been evaluated. From the UV absorption spectra of Mn2+, Co2+ and Ni2+ ions doped glasses, both direct and indirect optical band gaps have been calculated. The visible absorption spectra of Mn2+:glasses have shown a broad absorption band at 520 nm (6A1g(S) --> 4T1g(G)); with Co2+ ions one absorption band at 605 nm (4A2(4F) --> 4T1(4P)) and another at 1450 nm (4A2(4F) --> 4T1(4F)); and for Ni2+:glasses three absorption bands at 420 nm (3A2g(F) --> 3T1g(P)), 805 nm (3A2g(F) --> 1Eg(D)) and 880 nm (3A2g(F) --> 3T1g(F)) have been observed. For Mn2+:glasses, upon excitation with 262 nm, a green emission (539 nm) with a slight blue shift; and with 392 nm, a green emission (534 nm) with a slight red shift with Mn2+ ions concentration change (0.2-0.5 mol%) has been observed. This green emission has been assigned to (4T1(G) --> 6A1(S)) d-d transition of Mn2+ ions that are in tetrahedral co-ordination. For 0.5 mol% Co2+ ions doped glass, upon excitation with 580 nm, a red emission (625 nm) has been observed which originates from 2E(2G) --> 4A2(4F) transition of Co2+ ions in tetrahedral co-ordination. For Ni2+ ions doped glasses upon excitation with 420 nm, a green (577 nm) and red (670 nm) emissions are observed and are assigned to (1T2g(D) --> 3A2g(F)) and (1T2g(D) --> 3T2g(F)) d-d transitions of Ni2+ ions in octahedral co-ordination.     

Time-resolved study of solvent-induced recombination in photodissociated IBr-(CO2)n clusters

We report the time-resolved recombination of photodissociated IBr-(CO2)n (n = 5-10) clusters following excitation to the dissociative IBr-A' 2Pi12 state of the chromophore via a 180 fs, 795 nm laser pulse. Dissociation from the A' state of the bare anion results in I- and Br products. Upon solvation with CO2, the IBr- chromophore regains near-IR absorption only after recombination and vibrational relaxation on the ground electronic state. The recombination time was determined by using a delayed femtosecond probe laser, at the same wavelength as the pump, and detecting ionic photoproducts of the recombined IBr- cluster ions. In sharp contrast to previous studies involving solvated I2-, the observed recombination times for IBr-(CO2)n increase dramatically with increasing cluster size, from 12 ps for n = 5 to 900 ps for n = 8,10. The nanosecond recombination times are especially surprising in that the overall recombination probability for these cluster ions is unity. Over the range of 5-10 solvent molecules, calculations show that the solvent is very asymmetrically distributed, localized around the Br end of the IBr- chromophore. It is proposed that this asymmetric solvation delays the recombination of the dissociating IBr-, in part through a solvent-induced well in the A' state that (for n = 8,10) traps the evolving complex. Extensive electronic structure calculations and nonadiabatic molecular dynamics simulations provide a framework to understand this unexpected behavior.     

The photodissociation dynamics of ozone at 193 nm: an O(1D2) angular momentum polarization study

Polarized laser photolysis, coupled with resonantly enhanced multiphoton ionization detection of O(1D2) and velocity-map ion imaging, has been used to investigate the photodissociation dynamics of ozone at 193 nm. The use of multiple pump and probe laser polarization geometries and probe transitions has enabled a comprehensive characterization of the angular momentum polarization of the O(1D2) photofragments, in addition to providing high-resolution information about their speed and angular distributions. Images obtained at the probe laser wavelength of around 205 nm indicate dissociation primarily via the Hartley band, involving absorption to, and diabatic dissociation on, the B 1B2(3 1A1) potential energy surface. Rather different O(1D2) speed and electronic angular momentum spatial distributions are observed at 193 nm, suggesting that the dominant excitation at these photon energies is to a state of different symmetry from that giving rise to the Hartley band and also indicating the participation of at least one other state in the dissociation process. Evidence for a contribution from absorption into the tail of the Hartley band at 193 nm is also presented. A particularly surprising result is the observation of nonzero, albeit small values for all three rank K = 1 orientation moments of the angular momentum distribution. The polarization results obtained at 193 and 205 nm, together with those observed previously at longer wavelengths, are interpreted using an analysis of the long range quadrupole-quadrupole interaction between the O(1D2) and O2(1Deltag) species.     

Internal state distribution of the CF fragment from the 193 nm photodissociation of CFCl and CFBr

The dynamics of the 193 nm photodissociation of the CFCl and CFBr molecules have been investigated in a molecular beam experiment. The CFCl and CFBr parent molecules were generated by pyrolysis of CHFCl2 and CFBr3, respectively, and the CFCl and the CF photofragment were detected by laser fluorescence excitation. The 193 nm attenuation cross section of CFCl was determined from the reduction of the CF photofragment signal as a function of the photolysis laser fluence. The internal state distribution was derived from the analysis of laser fluorescence excitation spectra in the A 2Sigma+-X 2Pi band system. A very low degree of rotational excitation, with essentially equal A' and A" Lambda-doublet populations, and no vibrational excitation were found in the CF photofragment. The energy available to the photofragments is hence predominantly released as translational energy. The CF internal state distribution is consistent with the dissociation of a linear intermediate state. Considerations of CFCl electronic states suggest that a bent Rydberg state is initially excited.