IR multiple-photon excitation distribution probed by IR fluorescence

Vibrational fluorescence induced by IR multiple-photon excitation of hexafluorocyclobutene was measured as a function of laser frequencies. The width and shift of the inhomogeneous broadened fluorescence bands represent the excitation energy. The contrasting shapes of the excitation and previously measured chemical yield spectra are explained by the Poisson distribution of the molecules in the quasicontinuum.     

Laser multiphoton ionization of aromatic molecules in nonpolar liquids

The laser multiphoton ionization (MPI) of fluoranthene in tetramethylsilane (TMS) and of azulene in n-tridecane, n-pentane, 2,2,4,4-tetramethylpentane, TMS and tetramethyltin is reported. Three distinct types of MPI mechanisms have been identified: two-photon ionization, stepwise three-photon ionization and mixed two- and three-photon ionization. The stepwise three-photon process consists of two-photon excitation, relaxation to a lower lying excited state with a lifetime comparable to the laser pulse duration (for azulene this state is the S₂ while for fluoranthene both the S₁ and S₂ states) and subsequent ionization with the absorption of a third photon. The ionization threshold of azulene in each liquid has been determined and found to vary linearly with the V₀ of the liquid.     

Formation of selectivity in molecular isomerization by the IR multiphoton excitation

The formation mechanism of the selectivity of IR laser isomerization induced by vibrational multiphoton excitation is considered. The effective and highly selective isomerization of perfluorodimethyl ketene (CF₃)₂C=C=O into perfluoromethacrylic acid fluoride F₂C=C(CF₃)COF and perfluorocyclobutene into perfluorobutadiene upon pulse irradiation with a CO₂ laser and its second harmonic was performed. The conversion of (CF₃)₂C=C=O into F₂C=C(CF₃)COF was higher than 99%. A record-breaking conversion of 99.8% of the parent substance into the isomer was achieved in the case of perfluorocyclobutene isomerization into perfluorobutadiene. It was shown that the high selectivity of the laser-induced chemical reactions is mainly associated with the different levels of the vibrational excitation of the parent molecules and their isomers. The latter is due to the difference in the IR absorption spectra of different isomers, which allows for the excitation of the necessary component with a high selectivity.     

Laser intensity effects in the IR multiple-photon absorption of OsO4

The visible luminescence resulting from multiple-photon absorption of CO₂ laser radiation in OsO₄ depends upon the laser intensity as well as fluence. The use of single-mode laser pulses, shaped by electro-optic crystal switching, has enabled this intensity dependence to be determined quantitatively.     

Photoelectron imaging following 2 + 1 multiphoton excitation of HBr

The photodissociation and photoionization dynamics of HBr via low-n Rydberg and ion-pair states was studied by using 2 + 1 REMPI spectroscopy and velocity map imaging of photoelectrons. Two-photon excitation at about 9.4-10 eV was used to prepare rotationally selected excited states. Following absorption of the third photon the unperturbed F (1)Delta(2) and i (3)Delta(2) states ionize directly into the ground vibrational state of the molecular ion according to the Franck-Condon principle and upon preservation of the ion core. In case of the V (1)Sigma(+)(0(+)) ion-pair state and the perturbed E (1)Sigma(+)(0(+)), g (3)Sigma(-)(0(+)), and H (1)Sigma(+)(0(+)) Rydberg states the absorption of the third photon additionally results in a long vibrational progression of HBr(+) in the X (2)Pi state as well as formation of electronically excited atomic photofragments. The vibrational excitation of the molecular ion is explained by autoionization of repulsive superexcited states into the ground state of the molecular ion. In contrast to HCl, the perturbed Rydberg states of HBr show strong participation of the direct ionization process, with ionic core preservation.     

Effects of collective emission on multiphoton excitation and ionization near a three-photon resonance

We show that collective emission strongly affects excitation and the enhancement of multiphoton ionization near resonances involving odd numbers of photons. Such effects lead to striking shifts and broadening of resonantly enhanced multiphoton ionization signals near the odd photon resonance, and to a strong decrease in the ionization with increasing pressure.     

Emitter lifetime and velocity distribution in the collisionless IR multiphoton excitation of chromyl chloride

The collisionless infrared multiphoton exeitation of chromyl chlonde is studied systematically. An attempt is made to find the parentage of the induced visible emission.     

Direct observation of excited-state dynamics by hot UV absorption spectroscopy after IR multiphoton excitation

Fluoroethylcycloheptatriene has been irradiated by pulses from a TEA CO₂ laser. During and after the pulses, the hot UV absorption of the excited molecules was monitored. At very low gas pressures, time-resolved observation of the rate of unimolecular isomerization of the excited molecules was possible. By adding collision partners, stepwise collisional deactivation of excited molecules was also observed. By analysis of the transient spectra, the intra- and inter-molecular dynamics of the excited molecules was found to be quantitatively consistent with data from single-photon excitation experiments. The dependence of the observed dynamics on the laser fluence is demonstrated.     

Vibrational excitation following the Sls core ionization of CS

Ab initio non-relativistic spin-unrestricted Hartree-Fock calculations are performed on CS and its Sls core-ionized state. Geometrical relaxation is investigated. As in the corresponding first-row CO, relaxation greatly influences the vibrational band profile. The one-particle vibrational picture leads to bond-length shortening whereas relaxation and direct calculations indicate a slight bond-length increase, leading to a predicted small vibrational broadening.     

Laser intensity effects in the IR multiphoton decomposition of CF2HCl

Major intensity effects were observed in the collision-free CO₂ laser-induced dissociation of CF₂HCl utilizing real-time laser-excited fluorescence diagnostics. At constant fluence: increasing average pulse intensities by 6 increased dissociation yields 400 fold; pulse mode-locking caused 5–10 fold increases in yield. Induction times reflect threshold behavior. Collisions reduce laser intensity effects.     

Femtosecond multiphoton ionization of pyrrole

The photoionization dynamics of pyrrole are investigated by using a photoelectron imaging method and a tunable femtosecond laser. Two-photon nonresonant ionization experiments in the wavelength range from 261 to 298 nm indicate that the cation and neutral ground states have similar structures. The main vibrational excitation in the cation ground state is the v(8) mode. Two-photon absorption at 406 nm projects neutral pyrrole into a mixed state comprising the 1B(2) valence and 3p Rydberg states. Ionization from this mixed state mainly results in the overtone excitation of vibrational mode v(8) and v(9) of the cation state. In the wavelength range from 336 to 364 nm, a mixed state comprising the 3d/4s Rydberg and the 4A(1) valence states are populated by the absorption of two photons through vibronic coupling. The partition ratio among these states varies with the excitation wavelength, resulting in dramatic changes in both kinetic energy distributions and angular distributions. As the laser wavelength becomes shorter, from 336 to 314 nm, higher excited states, 3B(2), 5A(1), 6A(1), 7B(1) and 4B(2), can be populated. Photoelectron angular distributions provide supplementary verification of assignments. Our experiments indicate that femtosecond multiphoton ionization and photoelectron imaging methods are powerful tools for investigating short-lived intermediated excited states, which cannot be detected in nanosecond experiments.     

IR detection of H atoms produced by IR multiphoton dissociation

Hydrogen atoms produced by irradiation of alkenes with a focused CO₂ TEA laser react with Cl₂, forming vibrationally excited HCl, from which IR emission can be monitored. The application of this experimental technique to the study of H- atom reactions is discussed.     

Direct measurement of near-threshold rate constants for unimolecular dissociation of CF3I after IR multiphoton excitation

Excited-state populations of CF₃I after IR multiphoton excitation were monitored by time-resolved hot-band UV absorption spectroscopy. Using a calibration of the spectrum by shock-wave experiments, the absorption changes during the laser pulse are analyzed with respect to excited-state populations and dissociation at higher excitation energies. Dissociation of molecules near threshold is detected under collision-free conditions by absorption changes after the laser pulse. At higher pressures, absorption signals after the pulse are markedly influenced by energy transfer between excited and cold molecules. The measured dissociation rate constants near threshold are consistent with statistical calculations of k(E,J), showing pronounced rotational dependence.     

Infrared multiphoton excitation of small molecules

The collisionless infrared excitation by short CO₂ laser pulses of the molecules SO₂, OCS, NO₂, NH₃ and DN₃ is compared with that of larger molecules. The average number of photons absorbed per molecule and the fraction of molecules dissociated depends predominantly on the laser intensity, while for larger molecules with higher densities of vibrational states the excitation is primarily determined by the laser fluence.     

Two-frequency two-photon ionization of nascent PO(X2II) from the collision-free IR photolysis of dimethyl methylphosphonate

We report the detection of nascent PO produced via the collision-free IR photolysis of dimethyl methylphosphonate. Absorption throughout the B²Σ⁺ ← X²Π system is followed by excitation using 266 nm radiation, which results in PO⁺ + e. Spectral features due to spin-orbit excitation appear extremely “cold” relative to vibrations and rotations.     

Evolution of a system undergoing multiphoton ionization

We describe an efficient method for solving the time-dependent Schroedinger equation for an atomic system subject to an oscillating radiation field. The method is based on solving the Schroedinger equation in momentum space, which obviates the need to impose artificial boundaries, and facilitates the extraction of the rapidly varying part of the wavefunction. We present results of a test application to a one-dimensional system with atomic potential ?exp(?|x|/a ₀).     

Infrared multiphoton excitation of refractory metal clusters

Photoexcitation and photoionization experiments on small Tungsten and Niobium clusters were performed with a Q-switched Nd:YAG laser (1064 nm) and a reflectron type time-of-flight mass spectrometer. For low laser fluences the monomer and very small clusters do not show up in the mass spectra. Furthermore, the detected cluster ions show very asymmetric peak shapes caused by delayed ionization (thermionic emission). For high photon fluences photoions with up to charge state +3 could be detected.     

Detection and structural characterization of clusters with ultrashort-lived electronically excited states: IR absorption detected by femtosecond multiphoton ionization

The vibrational fingerprint of the electronically excited short-lived complex of 1-H-pyrrolo[3,2-h]quinoline:methanol was measured using femtosecond multiphoton ionization detected infrared (IR/fsMPI) spectroscopy under supersonic jet conditions. A cyclic doubly hydrogen-bonded structure of the cluster has been proven from the comparison of the measured vibrational spectrum with that calculated with density functional theory. The employed nsIR-fsUV double resonance scheme is shown to be an effective tool for structural analysis of precursors that undergo fast deactivation and/or photoreactions.