Mid-infrared absorption cross-sections and temperature dependence of CFC-113

The temperature dependence of the infrared absorption cross-sections of CFC-113 (1,1,2-trichlorotrifluoroethane) in a pure vapor phase has been recorded in the 600-1250 cm⁻¹ spectral region using Fourier transform spectroscopy. Spectra at 0.05 cm⁻¹ resolution have been used to derive the integrated band strengths of the five main absorption bands over a range of temperatures from 223 to 283 K. Our results show good agreement with previously published data. The new cross-sections will allow more accurate retrieval of atmospheric CFC-113 concentrations using infrared spectroscopic techniques.     

Line-by-line calculations of thermal infrared radiation representative for global condition: CFC-12 as an example

We estimate a current direct radiative forcing due to CFC-12 of 0.18 Wm^-2, which is likely to be the peak radiative forcing for CFC-12. Global measurements of CFC-12 show at present an almost negligible trend for CFC-12 and measurement in an industrialized region show evidence that the peak concentration is reached. It is expected that concentration of CFC-12 in industrialized regions begins to decline 1-3 years before the global concentration.Our radiative forcing calculations are based on a line-by-line model appropriate for simulation of global mean radiative forcing, including clouds and stratospheric temperature adjustment. The radiative forcing of 0.33 Wm^-2/ppbv is close to earlier published results for this compound. New spectroscopic measurements for CFC-12 are performed and compared to previously published results.     

A theoretical spectroscopic study of single ammonia molecules adsorbed on the surface of fcc-type argon clusters. Surface effects on the ν 2 vibration-inversion mode

Ammonia monomers have been adsorbed on argon clusters at low temperature K by Rohmund and Huisken [#!frfh97!#] using the pick-up technique. They measured the spectrum of the NH₃ molecules in the region of the umbrella mode. Two broad bands centered around 970 and 1000 cm^-1 with finer details were observed. The authors attempted to interpret the obtained spectrum on the basis of the free rotation motions of the molecules. In this paper semi-empirical atom-atom potential energy calculations are performed for the ammonia monomer adsorbed on a rigid face-centered-cubic (fcc)-type surface of the argon cluster. In the equilibrium position of the rigid molecule on the cluster surface the orientational potential energy surface exhibits two quasi-equivalent minima separated by a potential barrier of about 100 cm^-1. The symmetry of the molecular vibration-inversion double-well potential is destroyed; the inversion motion is then forbidden in the ground state. On the basis of the two adsorption orientations, the vibrational frequency shifts are calculated and the obtained infrared bar-spectrum agrees with the experimental one. Received 6 April 1999 and Received in final form 19 July 1999     

Computational studies of vibrational spectra and molecular properties of 6-methyluracil using HF, DFT and MP2 methods

Theoretical investigations of atomic charges, conformers, frontier molecular orbitals, molecular geometries, thermodynamic properties, hyperpolarizabilities and harmonic vibrational frequencies of 6-methyluracil (6MU) have been carried out using ab initio Hartree-Fock (HF), density functional theory (DFT) and second order M?ller-Plesset (MP2) methods. All calculations were performed using the GAMESS-US program package with the basis sets 6-31G(d,p) and 6-311G(d,p). FT-IR and Raman spectra of 6MU were recorded in the regions 50–4000 cm⁻¹ and 60–4000 cm⁻¹ respectively. Optimized geometries were obtained using the global optimization procedure. The calculated structural parameters for two conformers of 6MU have been compared with experimentally observed values. The energy barrier (ΔE=ELUMO-EHOMO) between the HOMO and LUMO is predicted on the basis of theoretical calculations. The simulated TD-DFT spectrum has been compared with experimental electronic spectrum for 6MU. The calculated potential energy distribution (PED) values have been utilized to perform vibrational assignment of the infrared and Raman spectra.     

Sub-Doppler laser absorption spectroscopy of the AΠi − XΣ (1, 0) band of CN: Measurement of the N hyperfine parameters in AΠ CN

Measurements of multiple rotational lines in the (1, 0) band of the A²Π_i − X²Σ⁺ “red” system of the cyanogen radical (CN) at sub-Doppler resolution are reported. The CN radical was produced by 193 nm photodissociation of NCCN (ethane dinitrile) and detected with a Ti:sapphire ring laser operating near 10 900 cm⁻¹. The sample was exposed to a weak, frequency-modulated probe beam and a strong, counterpropagating bleach laser beam. Demodulated probe laser signals display absorption and dispersion features derived from Doppler-free saturation of the hyperfine components as the laser scans across the central region of a Doppler-broadened rotational line spectrum. Hyperfine-resolved transition frequencies were combined with known ground-state X²Σ hyperfine term values to determine A²Π state hyperfine term values, which were analyzed in terms of an effective Hamiltonian for the A²Π state. All the expected hyperfine and ¹⁴N quadrupolar parameters were determined and their values analyzed in terms of a simple molecular orbital picture of the bonding in the radical. Higher sensitivity obtained with 400 kHz amplitude modulation of the bleach laser and additional phase-sensitive detection allowed hyperfine splittings in some rotational lines of ¹³C¹⁴N to be observed in natural abundance. Excited state hyperfine splittings were determined for a selection of rotational states, but not enough to determine the ¹³C hyperfine parameters.     

Spectroscopic and lasing characterisation of a dicarbazovinylene-MEH-benzene dye

The dye 1,4-bis(9-ethyl-3-carbazovinylene)-2-methoxy-5-(2′-ethyl-hexyloxy)-benzene (abbreviated 2CzV-MEH-B) dissolved in tetrahydrofuran (THF) and as neat film is characterised by optical absorption and emission spectroscopy. The absorption and stimulated emission cross-section spectra, the fluorescence quantum distributions, fluorescence quantum yields, degrees of fluorescence polarisation, and fluorescence lifetimes are determined. A lasing characterisation is carried out by pumping with single second harmonic pulses of a mode-locked ruby laser (wavelength 347.15 nm, pulse duration 35 ps). The excited-state absorption at the pump laser wavelength is determined by saturable absorption measurements. Laser oscillation of the dye in THF in a rectangular cell is achieved by transverse pumping using the uncoated cell windows for light feedback. From the emission behaviour around threshold the excited-state absorption cross-section spectrum in the laser active spectral region is extracted. The wave-guided travelling-wave lasing behaviour of the dye as neat film is studied by analysis of the amplification of the transverse pumped spontaneous emission. Surface emitting distributed-feedback lasing was achieved with a neat film on corrugated second-order periodic gratings.     

The fundamental band ν2 of D2CO

The ν₂ band of D₂¹³CO in the region of 1570-1760 cm⁻¹ has been analyzed with high accuracy. The limits of the quantum numbers J and K_a are 50 and 16, respectively. The number of the assigned transitions is 3858. A local anharmonic resonance ν₂/2ν₄ at K_a =  8-12 was observed. The Watson’s A-reduced Hamiltonian and anharmonic resonance term were fitted to the observed transitions. The fit resulted in the band center and rotational parameters of the ν₂ band as well as the effective parameters for the 2ν₄ band and anharmonic resonance parameter. The rms deviation of the transitions in the ν₂ band was 0.000364 cm⁻¹.     

Infrared absorption-edges of molecular nonlinear optical crystals: an <Emphasis Type="Italic">ab initio</Emphasis> calculation

A theoretical model suitable for calculating infrared absorption-edges of molecular nonlinear optical (NLO) crystals is introduced from high-level calculations of molecular vibrational spectra. The model is useful for elucidating the relationship between the molecular vibration and macroscopic absorption edges on the IR side of organic nonlinear optical crystals. The first-principle ab initio method carries out the calculations of IR absorption-edges of several typical molecular NLO crystals. These molecular NLO crystals include urea, 2-methyl-4-nitroaniline (MNA), meta-dinotrobenzene (MDNB), 3-methyl-4-methooxy-4^′-nitrostilbene (MMONS), and 3-hydroxyl-4^′-nitrostilbene (HMONS). The calculated results are compared with the measurements and good agreement is found between them. The experimentally unknown values of IR absorption-edges of some new synthesized crystals are predicted. The theoretical analyses of the structural origins of IR absorption cut-offs are discussed. The results are helpful for the molecular simulation and design of potential infrared molecular NLO crystals. Received: 9 April 2002 / Accepted: 18 July 2002 / Published online: 28 October 2002 RID="*" ID="*"Corresponding author. Fax: +86-591/3714946, E-mail: wkc@ms.fjirsm.ac.cn     

Second-harmonic and sum-frequency generation in AgGaSe2 with tunable waveguide CO2 lasers

A tunable source is described, giving extensive coverage of a spectral region around 2000 cm^–1. A frequency self-calibration routine allows for the recording of Doppler-limited absorption profiles with an absolute accuracy of better than 10 MHz. The applicability of the source is demonstrated through measurements on the¹²C¹⁶O,¹²C¹⁷O, and¹²C¹⁸O isotopomers. Collision-broadening parameters and line strengths are determined, some of the data showing evidence of motional narrowing. Sensitivity limits are determined for linear absorption measurements as well as for photoacoustic absorption, and the feasibility of monitoring all three isotopomers with ppm sensitivity is demonstrated.Work supported by the Danish Science Research Council under grants no. 11-6866, 11-0116, and 11-0920     

New analysis of the Douglas-Herzberg system (A1Π- X1Σ+) in the CH+ ion radical

Three bands of the A¹Π- X¹Σ⁺ system in the ¹²CH⁺ ion radical have been rephotographed under high resolution as an emission spectra using a Geissler-type discharge tube. The conventional technique of spectroscopy has been implemented. Using the Th lines as a standards, as well as an interferometric comparator equipped with a photoelectric scanning device, the 0-0 , 0-1 and 2-1 bands have been reanalyzed. By means of much longer bands (J_max = 17 in the Q(J) branch of the 0-0 band; J_max = 16 in the R(J) branch of the 0-1 band; J_max = 14 in the P(J) and Q(J) branches of the 2-1 band), than have been observed so far, as well as the merged calculations, using another five bands given by Carrington et al. [A. Carrington, D.A. Ramsay, Phys. Scripta 25, 272 (1982)] additionally, more accurate molecular constants for the X¹Σ⁺ state, the improved reduced band system origin T_e = 24118.726 (14) cm^-1 as well as for the first time the equilibrium molecular constants with their one standard deviation for the A¹Π state in the CH⁺ molecule have been computed: ω_e'=1864.402(22), ω_ex_e'=115.832(14), ω_ey_e'= 2.6301(24), B_e'=11.88677(72), α_e'= 0.9163(18), γ_e'= -2.29(12)×10^-2, ε_e'= 4.95(20)×10^-3, D_e'=1.92960(31)×10^-3, β_e'= 1.0733(50)×10^-4, δ_e'= -1.312(16)×10^-5, , α_qe'= -3.14(16)×10^-3, and q_De'= -2.20(14)×10^-5 cm^-1. Only in our research the addition to the zero-point energy Y'₀₀=-1.9430 cm^-1 and cm^-1 have been calculated. The equilibrium bond lengths of r'_e=1.235053(37) ? and ? for the A¹Π and X¹Σ⁺ states, respectively have been computed. Full quantum-mechanics characteristic of the A-X bands system in the ¹²CH⁺ molecule, i.e. RKR turning points, the Franck-Condon factors and r-centroids have been obtained. Dissociation energies D_e^{X1 Σ+}=(38470± 3503) cm^-1 and D_e^{A1 Π}= (14415 ±3509) cm^-1 for the molecule under consideration have been estimated.     

On the accurate determination of pressure- induced line shifts in the 2ν<Subscript>3</Subscript> band of H<Subscript>2</Subscript>O at 1320 nm

A simple technique is demonstrated for the accurate determination of pressure-induced line shifts of water in air. High- and low-pressure water samples are simultaneously probed on selected overtone transitions at 1.32 μm using a current-modulated distributed-feedback diode laser and harmonic detection. The resultant profiles yield an average line shift of -293±30 MHz/atm for the 3,3,0 (002)2,2,1 (000)transition at 227251 GHz and -134±7 MHz/atm for the 3,2,1 (002)2,1,2 (000) transition at 227027 GHz. Comparisons are made between first- and second-harmonic detection, and wavelength- and frequency-modulation regimes. The effect of modulation broadening on the returned line shifts is quantified. Received: 12 August 2002 / Revised version: 21 October 2002 / Published online: 8 January 2003 RID="*" ID="*"Corresponding author. Fax: +44-01865/275410, E-mail: gus.hancock@chemistry.ox.ac.uk     

Optical absorption of 1-phenyl-3-methyl-1H-pyrazolo[3,4-b]quinoline derivatives: Molecular dynamics modeling

Paper deals with quantum chemical modeling of the optical absorption spectra of 6-fluoro, 7-trifluoromethyl, 6-cyano, 6-carboethoxy and 6-tert-butyl derivatives of 1-phenyl-3-methyl-1H-pyrazolo[3,4-b]quinoline. The calculations are performed by means of the semiempirical quantum chemical methods (AM1 or PM3) applied to the equilibrium molecular conformation in vacuo (T = 0 K) or molecular dynamic (MD) trajectories as obtained within fragmental or total MD simulations at T = 300 K. The results of these calculations are compared with the measured spectra of optical absorption. The quantum chemical analysis show that the dynamics of the methyl, trifluoromethyl, carboethoxy and tert-butyl groups practically does not influence the absorption spectra whereas the strongest their modifications are found to be related with dynamics of the aromatic group. The semiempirical method AM1 in combination with MD simulations gives for all dyes the best agreement between the calculated and measured spectral positions of absorption bands. In most cases the quantum chemical calculations describe properly the trends of their changes depending on the lateral substituent.     

THz spectrum of monodeuterated methane

We report new measurements of the rotational spectrum of monodeuterated methane (CH₃D) in the range of 690-1200 GHz which allow for an accurate prediction of all lines in the range of the high-resolution spectrometer of the Herschel Space Observatory. Comparison is also made with the previous analysis based on infrared combination differences. Three lines of ¹³CH₃D were measured in natural abundance.     

FT-FIR-spectrum and the ground state constants of D2CO

The ground state spectrum of the formaldehyde D₂¹³CO molecule in the range from 25 to 360 cm⁻¹ has been recorded by a Fourier transform infrared spectrometer. The quantum number limits of the assigned transitions are J = 6-54 and K_a = 0-16. The data was fitted into Watson’s A- and S-reduced Hamiltonians in I^r-representation up to eighth order. The determinable constants calculated from both reductions are compared. The standard deviation of the far infrared data is 3.0 MHz. The spectroscopic constants are also calculated to high accuracy at the CCSD(T)/cc-pVQZ level of ab initio theory and agree well with the experimental ones.     

Electronic states of neutral and ionized tetrahydrofuran studied by VUV spectroscopy and ab initio calculations

The electronic spectroscopy of isolated tetrahydrofuran (THF) in the gas phase has been investigated using high-resolution photoabsorption spectroscopy in the 5.8–10.6 eV with absolute cross-section measurements derived. In addition, an electron energy loss spectrum was recorded at 100 eV and 10° over the 5–11.4 eV range. The He(I) photoelectron spectrum was also collected to quantify ionisation energies in the 9–16.1 eV spectral region. These experiments are supported by the first high-level ab initio calculations performed on the excited states of the neutral molecule and on the ground state of the positive ion. The excellent agreement between the theoretical results and the measurements allows us to solve several discrepancies concerning the electronic state spectroscopy of THF. The present work reconsiders the question of the lowest energy conformers of the molecule and its population distribution at room temperature. Electronic supplementary material  Supplementary Online Material     

Terahertz absorption spectrum of D2O vapor

The absorption spectrum of D₂O vapor from 0.2 to 2.0 THz (6.7-67 cm⁻¹) which is associated with rotational modes was measured at one atmosphere using terahertz time-domain spectroscopy (THz-TDS). The linewidth and collisional dephasing times were measured for 26 pure rotational transitions in the ground vibrational state (0 0 0). The temperature dependence of the linewidth (Δν) behaves as Δν ∼ T^−3/4 and the linewidth decrease with increasing temperature is attributed to the 1/r⁶ force of interaction between colliding D₂O molecules.     

Middle infrared luminescence of Tb in silver halide crystals and fibers

The optical absorption and the luminescence emission were investigated in AgCl_xBr_1−x crystals (0<x<1) doped with Tb³⁺ ions and in fibers extruded from these crystals. Strong luminescence emission in the middle infrared (MIR) in the spectral range 4.2-5.6 μm was observed for the first time in such crystals and fibers.¹ Various optical parameters were calculated for the Tb³⁺-doped crystals, using the Judd-Ofelt approximation. The measured and the calculated results have indicated that these doped crystals could be used for the development of solid-state lasers or fiber lasers operating in the middle infrared.     

Systematic analysis of the Fourier transform spectrum of CH3OH between 400 and 950 cm

We have investigated a high-resolution Fourier transform (FT) absorption spectrum of the ¹³CH₃OH isotopomer of methanol from 400 to 950 cm⁻¹ with the “Ritz” program. We present the assignments of 7160 transitions, 3021 of which belong to A-symmetry, and 4139 to E-symmetry. These transitions occur between states labeled by K quantum numbers up to 14, and by torsional quantum numbers n up to 4. The “Ritz” program evaluated the energies of the 4684 involved levels with an accuracy of the order of 10⁻⁴ cm⁻¹. All of the assigned lines correspond to transitions involving torsionally excited levels within the ground small-amplitude vibrational state.     

Middle-infrared luminescence of Nd ions in silver halide crystals

The optical absorption and the luminescence emission in the middle infrared (mid-IR) were investigated in AgCl_xBr_1−x crystals doped with Nd³⁺ ions. Strong luminescence emission, in the spectral range 4.5-5.8 μm, in mid-IR was observed for the first time in Nd³⁺-doped silver halide crystals. Various optical parameters were calculated for the Nd³⁺-doped crystals, using the Judd-Ofelt approximation. The measured results and the calculated parameters indicate that these doped crystals could be used for the development of mid-IR solid-state lasers or mid-IR fiber lasers.     

Upconverted 5d-4f luminescence from Er and Nd ions doped into fluoride hosts excited by ArF and KrF excimer lasers

We report on observation of upconverted VUV luminescence due to 5d-4f radiative transitions in Er³⁺ and Nd³⁺ ions doped into some fluoride crystals, under excitation by ArF and KrF excimer lasers, respectively. Only spin-forbidden 5d-4f luminescence of Er³⁺ (at 165 nm) was detected from the LiYF₄:Er³⁺ crystal whereas both spin-forbidden (at 169 nm) and spin-allowed (at 160.5 nm) components are observed from the BaY₂F₈:Er³⁺ crystal, the latter being much weaker than in the case of one-photon excitation. Nd³⁺ 5d-4f luminescence at 180 and 173 nm has been detected from the LiYF₄:Nd³⁺ and LaF₃:Nd³⁺ crystals, respectively. The shift of short-wavelength edge of 5d-4f emission spectra towards longer wavelengths is observed under temperature increase from 15 to 293 K. The observed effects in the spectra of Er³⁺ and Nd³⁺ doped crystals were interpreted as a result of reabsorption of 5d-4f luminescence escaping from the bulk of the crystals.