Parametric four-wave mixing in the H2Σ+,H′2Π(v′=0) states of NO

2 Σ⁺,H^′2Π(v^′=0)←X²Π(v^′′=0) two-photon transition of NO, both near-infrared and vacuum ultraviolet radiation were emitted along the laser propagation direction. The analyses of emission and excitation spectra revealed that the parametric four-wave mixing (PFWM) process coexisted with amplified spontaneous emission. Polarization properties of the IR radiation are found to be dependent on the rotational levels. Pressure and laser power behaviors of the generated waves were reported. The mechanism of PFWM was discussed in terms of selection rules of the relevant ro-vibronic transitions. Received: 19 September 1996/Revised version: 27 January 1997     

Hyperfine interactions in molecules through laser spectroscopy

The infrared and millimeter wave spectroscopy, laser Stark spectroscopy, and beam maser spectroscopy of CH₃CN and its isotopic species will be discussed. The beam maser spectroscopy and hyperfine structure of molecules like NCCCD, ClCCD and CH₃CCH are reviewed. The laser magnetic resonance and hyperfine structure in CF, CH and CH₂ free radicals will be discussed. The Lamb dip spectroscopy and laser-induced fluorescence in I₂ involving theB ³Π(0 _u ⁺ ) state are reviewed with special reference to its hyperfine structure. The splitting of the rotational levels of N ₂ ⁺ in itsX ²Σ _g ⁺ andB ²Σ _u ⁺ states due to hyperfine interactions (along with the hyperfine structure) in laser-induced fluorescence in theB−X transition is discussed. Recent results obtained in the laser photo-acoustic spectrum of ICl in the transitionX ¹Σ⁺ −A ³Π₁ will be presented and the possibility of the use of this technique in studying the hyperfine structure will be discussed.     

The use of rovibrationally excited NO photofragments as trace nitrocompounds indicators

A one-color laser performs photolysis of nitrocompounds and laser-induced fluorescence to monitor the generated NO photofragments and to sensitively detect vapor trace amounts of nitrocompounds. The NO is monitored via excitation and emission through A²Σ⁺(v^′=0)?X²Π(v^′′=2-0) and A²Σ⁺(v^′=0)?X²Π(v^′′=0,1) transitions, respectively. It is found that NO photofragments populate the vibrationless ground state and also the first two vibrationally excited states. The analytical performance of the method is demonstrated on 2,4 dinitrotoluene (DNT) via excitation through A²Σ⁺(v^′=0)?X²Π(v^′′=2). The achieved limits of detection are 3.7 and 2.7 parts per billion (ppb) by weight of gaseous DNT in 100 and 500 Torr of air, for 30 s integration time. The application of this scheme for trace nitrocompound detection has the advantage that no background of ambient ground-state NO interferes and that the fluorescence is collected at shorter wavelengths than the exciting radiation, precluding background fluorescence. Received: 18 August 1999 / Revised version: 22 November 1999 / Published online: 8 March 2000     

Parametric four-wave mixing in the 3d and 4d Rydberg states of NO

2 Σ⁺,H^′ 2Π^±(v^′=2), and 4dσ,πO²Σ⁺,O^′ 2Π^±(v^′=0) Rydberg states of NO molecules are described. The analyses of the two-photon excitation functions and infrared emission spectra revealed that only the ²Π^- component was involved in PFWM. This is in good accordance with the absence of amplified spontaneous emission (ASE) in the ²Σ⁺ and ²Π⁺ components due to their predissociative character. Results provide some support for the mechanism that the generation of the vacuum ultraviolet radiation was brought by PFWM in which ASE served as a third driving wave. Received: 6 January 1998     

Time-dependent wave packet theoretical study of femtosecond photoelectron spectra and coupling between the A<Superscript>2</Superscript>Σ<Superscript>+</Superscript> and B<Superscript>2</Superscript>Π states of the NO molecule in a strong laser field

In this work, the femtosecond time-resolved photoelectron spectra and the coupling between the A²Σ⁺ and B²Π states of the NO molecule in a strong laser field have been investigated by the time-dependent wave packet method. We demonstrate that the weak coupling between the A²Σ⁺ and B²Π states of NO plays a key role on the peak centered at 0.37 eV of the photoelectron spectra in the 2+1’ channel.     

Determination of the helium-4 mass in a Penning trap

The determination of the rotational quadrupole alignment of diatomic molecules via REMPI detection is investigated. In this process a high focal intensity usually increases the detection probability. At high intensities the AC Stark effect may cause a splitting of the normally degenerate m_J sublevels of a rotational state J beyond the spectral width of the exciting radiation. This leads to a selective detection of only certain m_J states with the consequence that deduced alignment factors can be misleading. From the theoretical considerations line profiles are explicitly calculated for dynamic polarizabilities which represent the B ¹Σ⁺ _u←X ¹Σ⁺ _g transition of H₂, in order to fit an experimental (3+1) REMPI spectrum and to predict (1+1') line shapes as a function of laser intensity. It is further shown that the deduced quadrupole alignment factor A ₀ ⁽²⁾ is significantly changed by the second order AC Stark effect when the intensities are chosen high enough to observe asymmetric broadened line profiles. Different combinations of relative linear polarizations of the exciting and ionizing laser beams are discussed. Received 1st August 2000 and Received in final form 2 May 2001     

Time-resolved Stark effect in rapidly varying fields

The cycle-averaged ac Stark effect associated with the ^[ A _]2Σ⁺v^′=2?^[ X _]2Π1/2v^′=0 two-photon absorption of NO at intensities between 7.7 and 15.2 TW cm^-2 has been characterized in real time through a synergic combination of bichromatic laser experiments and quantum-dynamics calculations. Measurements of the fluorescence emitted by the Rydberg ^[ A _]2Σ⁺v^′=2 level as a function of time between Stark and probe components of a bichromatic field exhibit a characteristic evolution in temporal peak structure with Stark-field intensity, which is interpreted in terms of a time-dependent Floquet analysis of the laser–matter interaction. The experimental observations are consistent with a dynamic Stark shift of Δε_s(ω₁,ω₂)≤0.23 eV of the optical transition at these intensities. Received: 18 January 2002 / Revised version: 6 March 2002 / Published online: 24 April 2002     

Emission spectroscopy of the A<Superscript>1</Superscript>Π–X<Superscript>1</Superscript>Σ<Superscript>+</Superscript> system of AlH

The high-resolution emission spectrum of the A¹ Π–X¹Σ⁺ transition of AlH was observed in the 18 000–25 000 cm^-1 spectral region using a conventional spectroscopic technique. The AlH molecules were excited in an Al hollow-cathode lamp filled with a mixture of Ne carried gas and a trace amount of NH₃. The emission from the discharge was observed with a plane grating spectrograph and recorded by a photomultiplier tube. In total 163 transition wave numbers belonging to six bands (0-0,1 and 1-0,1,2,3) were precisely measured and rotationally analysed. In the final fit the present data have been combined with available high-resolution measurements of the vibration-rotation bands by White et al. [J. Chem. Phys. 99, 8371 (1993)]. This procedure enabled extracting molecular constants for the A¹ Π and X¹ Σ⁺ states of AlH. A very slight local perturbation has been discovered in the v=1 vibration level of the A¹ Π state at J=5. This was probably caused by the interaction with the a³Π state.     

Fluorescence studies of CS2 and SO2 at 121.6, 73.6–74.4 and 58.4 nm

The fluorescence spectra of CS₂ and SO₂ have been studied at three incident photon wavelengths of 121.6, 73.6–74.4 and 58.4 nm and relative production cross sections for different product states have been measured. The CS(A ¹Π→X ¹Σ⁺) system between 240 and 290nm has been obtained when CS₂ is photoexcited at 121.6nm whereas CS ₂ ⁺ (B ²Σ _u ⁺ →X ²Π _g ) and CS ₂ ⁺ (A ²Π _u →X ²Π _g ) systems have been produced between 276 and 295 and 437 and 555nm respectively when excited by both the incident photon wavelengths of 73.6–74.4 and 58.4nm. The fluorescence spectra of SO₂ obtained at 121.6 and 73.6–74.4nm include the vibrational bands of SO(A ³Π→X ³Σ⁻) and SO(B ²Π⁻→X ³Σ⁻) systems from 240 to 268 and 268 to 442nm respectively whereas the emission spectrum at 58.4nm, has contributions from the two SO systems and SO⁺(A ²Π→X ²Π) system. In all these emission spectra, the fluorescence bands of different systems have been analyzed and their relative production cross sections have been measured. The results obtained in the present investigations have been compared with a few recent reliable measurements reported in literature.     

Tunable KrF laser-induced fluorescence of C2 in a sooting flame

2 in a flame, excited by a tunable KrF laser near 248 nm. The first comprises several P and R lines of the (1,0) band of the e ³Π_g-a ³Π_u Fox–Herzberg system, with fluorescence bands extending past 350 nm. The second is the band head region of the (7,1) band of the D ¹Σ_u ⁺←B^′ 1Σ_g ⁺ system, with fluorescence at 232 nm from D to the X ¹Σ_g ⁺ ground state. Neither band has been previously observed in any environment. The flame in these experiments is highly sooting, and the C₂ seen here is likely produced by laser vaporization of the soot with subsequent laser photolysis of a C₂ precursor. In a rich flame, this fluorescence could cause interferences in other studies such as KrF laser Raman scattering. Moreover, signal level calculations suggest native C₂ near 10 ppm could be readily observed using the Fox–Herzberg excitation. Raman measurements of major species (X≥0.01) in the same flame, using the KrF laser, are in good agreement with a model prediction. Received: 2 April 1998/Revised version: 8 June 1998     

Vibrational analysis of Fourier transform spectrum of the A3Π0-X1Σ+ and B3Π1-X1Σ+ transitions of indium monobromide

The emission spectrum of InBr molecule has been recorded in the region 350–400 nm on BOMEM DA8 Fourier transform spectrometer at an apodized resolution of 0.06 cm⁻¹ using microwave excitation technique. About 61 violet degraded and single headed bands have been recorded and are classified into two band systems, viz. A³Π₀-X¹Σ⁺ and B³Π₁-X¹Σ⁺. A few new bands have been observed and are fitted in the vibrational schemes of the two systems. Revised vibrational constants have been determined. The vibrational assignments have been confirmed by observing isotope effect due to InBr⁸¹ in the 30 bands of the A³Π₀-X¹Σ⁺ system and 19 bands of the B³Π₁-X¹Σ⁺ system. The analysis is further supported by calculating the Franck-Condon factor for InBr⁷⁹ and InBr⁸¹ molecules. The following vibrational constants (in cm⁻¹) have been determined from the analysis:      

Radiative lifetimes of the NaRb C(3)1Σ+ state: experiment and theory

Radiative lifetimes for 2≤v^′≤44 rovibronic C¹Σ⁺ state levels of NaRb and quenching collision cross-sections with Rb atoms have been directly measured in a thermal cell by detecting time resolved laser induced fluorescence after pulsed excitation. Many body multipartitioning theory was applied to calculate C¹Σ⁺-X¹Σ⁺ and C¹Σ⁺-A¹Σ⁺ transition dipole moments. The relevant ab initio matrix elements were converted to the C¹Σ⁺ state radiative lifetimes. The strong spin-orbit A¹Σ⁺∼ b³Π coupling effect on the total C → A transition probabilities and lifetimes of the C¹Σ⁺ state is discussed. The measured radiative lifetimes show a decrease from 61 to 34 ns as the v^′ values increase, the results being in good agreement with calculations. The averaged collisional quenching cross-section value σ=(3±1)×10^-14 cm² was determined for NaRb (C¹Σ⁺) + Rb collisions from the Stern-Volmer plots.     

Two-photon optogalvanic detection of theF′(O u + ) ion pair state of I2

Two-photon transition inF′(O _u ⁺ ) ion pair state of iodine from theB ³Π _Ou ⁺ state is detected for the first time using laser optogalvanic spectroscopy. TheB ³Π _Ou ⁺ is populated by a d.c. discharge running at constant voltage.     

Calculation of the spectroscopic constants for the electronic states A1Σ u+ , B1Πu, C1Πu, D1Σ u+ , and E1Σ u+ of the cesium dimer

The vibrational, rotational, and centrifugal distortion constants have been calculated for the electronic states A ¹Σ _u ⁺ , B ¹Π_u, C ¹Π_u, D ¹Σ _u ⁺ , and E ¹Σ _u ⁺ of the Cs₂ molecule. The calculation was performed on the basis of the semiempirical potential energy curves constructed in this paper. The calculated spectroscopic constants are compared with the experimental data. Original Russian Text ? A.D. Smirnov, 2007, published in Optika i Spektroskopiya, 2007, Vol. 102, No. 1, pp. 23–27.     

Hydroxyl tagging velocimetry (HTV) in experimental air flows

 The new nonintrusive instantaneous molecular flow tagging method, hydroxyl tagging velocimetry (HTV), previously demonstrated only for high-temperature reacting flows, is now demonstrated in low-temperature (300 K) ambient air flowfields. Single-photon photodissociation of ground-state H₂O by a ∼193-nm ArF excimer laser ‘writes’ very long grid lines (>50 mm) of superequilibrium OH and H photoproducts in a room air flowfield due to the presence of ambient H₂O vapor. After displacement, the positions of the OH tag lines are revealed through fluorescence caused by A²Σ⁺ (ν^′=0)?X²Π_i (ν^′′=0) OH excitation using a pulsed frequency-doubled dye laser with an operating output wavelength of ∼308 nm. The dye ‘read’ laser accesses the strong Q₁(1) line, compensating for the relatively weak 193-nm absorption of room-temperature H₂O. The weak absorption of ground vibrational state H₂O has previously precluded the use of HTV at low temperatures, since previous HTV systems relied on a KrF excimer ‘read’ laser that could only access a weak (3?0) OH transition. The instantaneous velocity field is determined by time-of-flight analysis. HTV tag lifetime comparisons between experimental results and theoretical predictions are discussed. Multiple-line tag grids are shown displaced due to an experimental air flowfield, thus providing 2-D multipoint velocity information. Due to the instantaneous nature of the HTV tag formation, HTV is particularly suitable for, but not limited to, a variety of fast flowfield applications including nonreacting base flows for high-speed projectiles and low-temperature hypersonic external or internal flows. Received: 3 July 2001 / Revised version: 6 November 2001 / Published online: 17 January 2002     

Laser photoacoustic spectroscopy of iodine molecule: Single and two-photon absorption

Photoacoustic spectroscopy of iodine molecule has been studied in gas phase using nitrogen laser-pumped tunable dye laser. The experiment yielded the vibrational spectrum corresponding toX ¹Σ⁺(0 _g ⁺ )→B ³Π(0 _g ⁺ ) transition up to the convergence limit. The photo-acoustic spectrum in the region 17580–18850 cm⁻¹ is presented along with the vibrational analysis. Five of the vibrational bands reported earlier by Venkateswarlu, Kumar and McGlynn have been partially resolved and the structure of one of them has been analyzed and shown to be due to an overlap of (14, 2) and (12, 1) bands. The analysis was based on a comparison with the highly resolved spectrum of Gerstenkorn and Luc. The structure observed in the region 20200–20750 cm⁻¹ which is beyond the convergence limit of the transitionX ¹Σ⁺(0 _g ⁺ )→B ³Π(0 _u ⁺ ) has been analyzed as due to two-photon absorption. Most of the bands could be assigned to two transitions both originating in the ground state and terminating in two different electronic states 1 _g andE(0 _g ⁺ ), atT _e=40821 cm⁻¹ (orT ₀=41355 cm⁻¹) andT _e=41411 cm⁻¹ (orT ₀=41355 cm⁻¹) respectively.     

High resolution optogalvanic study in nitrogen discharge

Doppler limited high resolution spectrum in the wavelength region 17224 to 17236 cm⁻¹ of the first positive system (B ³Π _g −A ³Σ _u ⁺ ) of the N₂ molecule is recorded by optogalvanic spectroscopic technique using a single mode ring dye laser. It is observed that the intensity and line width of the rotational line increase with the discharge current. Dependence of the collision broadening coefficient on the current was also evaluated.     

Spectroscopic study of rotational energy distribution of BH (A 1Π) and electronic excitation temperature determination

Emission spectra of BH(A ¹Π-X ¹Σ⁺) system were recorded and studied using a low pressure (3.0 torr) arc in flowing hydrogen and argon + hydrogen mixture. The rotational distributions in theA ¹Π state determined from the intensities of rotational lines for the 0–0 band of theA-X system conforms to a Maxwellian distribution with effective rotational temperature of 1000 ± 50°K. Intensities of Balmer lines of hydrogen were measured and used to determine electronic excitation temperature which was found to be around 2000°K.     

Cavity ring-down spectroscopy of photochemically produced NaH for the determination of relative dipole transition moments

-30 Cm of isolated lines in the A¹Σ⁺←X¹Σ⁺ NaH transition band were measured. Received: 18 November 1996/Revised version: 10 May 1997