Nature of the Electron Excited States and Energy Transfer in Bichromophore Coumarin Molecules

Results of experimental and theoretical research for three bichromophore molecules, trans-stilbene-CH₂-coumarin 120 (I), 4-methylumbelliferone-CH₂-UC 17, and 4-(3-fluoro)-methylumbelliferone-CH₂-UC 17 (II, III), are presented. Schemes of photophysical processes in the bichromophore molecules based on quantum chemical calculations by the INDO method and theory of radiationless transitions in polyatomic organic molecules are suggested. After optical excitation to the strong donor absorption band, the fast internal conversion processes develop there. As a result, the molecule is found in the S ₁ ^* -state localized on the acceptor moiety. It is shown that a mechanism of intramolecular transfer energy in bichromophores different from that proposed by Förster may be realized. Excitation energy, initially located on D, will be transferred from the donor moiety to the acceptor chromophore in convenience of the internal conversion process. The intramolecular electronic energy transfer from energy donor to energy acceptor may be interpreted as the internal conversion process. The rate constants of internal conversion are calculated.     

Evaluation of ammonia absorption coefficients by photoacoustic spectroscopy for detection of ammonia levels in human breath

Photoacoustic spectroscopy represents a powerful technique for measuring extremely low absorptions independent of the path length and offers a degree of parameter control that cannot be attained by other methods. We report precise measurements of the ammonia absorption coefficients at the CO₂ laser wavelengths by using a photoacoustic (PA) cell in an extracavity configuration and we compare our results with other values reported in the literature. Ammonia presents a clear fingerprint spectrum and high absorption strengths in the CO₂ wavelengths region. Because more than 250 molecular gases of environmental concern for atmospheric, industrial, medical, military, and scientific spheres exhibit strong absorption bands in the region 9.2–10.8 μm, we have chosen a frequency tunable CO₂ laser. In the present work, ammonia absorption coefficients were measured at both branches of the CO₂ laser lines by using a calibrated mixture of 10 ppm NH₃ in N₂. We found the maximum absorption in the 9 μm region, at 9R(30) line of the CO₂ laser. One of the applications based on the ammonia absorption coefficients is used to measure the ammonia levels in exhaled human breath. This can be used to determine the exact time necessary at every session for an optimal degree of dialysis at patients with end-stage renal disease.     

Infrared laser stark shift spectroscopy in ammonia

The Stark effect in ammonia has been theoretically and experimentally analyzed using lead salt tunable diode laser absorption spectroscopy and CO₂ laser absorption spectroscopy of several absorption lines around 1050 cm^–1 applied to an all-optical sensor for measuring of electric field strength. Measurements of the Stark splitting effect of theaR(5,K) ammonia lines forK=1–5 as well as for the sR(3,K) lines forK=0–3 have been made at Doppler broadening pressures and for several different electric field strengths. Theoretical electric field dependent energy levels have been evaluated by diagonalization of a 6×6 energy matrix constructed using both electric field independent and dependent terms. From the theoretical analysis the resolution can be predicted and optimized both in the Doppler broadened and in the pressure broadened regimes. The predicted resolution is 0.5% at an electric field strength of 20 kV/cm. The theoretical calculations and the experimental data recorded with the tunable diode laser system were compared with independent measurements made with a CO₂ laser system. The agreement between experimentally recorded and theoretically calculated spectra is good which indicates that the theoretical model is satisfactory for our purposes. The contribution from the normally forbidden ssR(5, 3) ammonia line to the absorption at theP(12) CO₂ laser line in the 9 m band is briefly discussed.     

The influence of mixed nano-Al2O3+CuO catalysts that are initial radiation in air environment on the surface impact in the oxidation processes

ABSTRACT

In this paper, the oxidation/conversion process of carbon monoxide (CO) has been examined under various temperatures on the surface of three types of catalysts (TAl₂O₃, TAl₂O₃+CuO and RTAl₂O₃+CuO). The catalyst samples have been exposed to γ-rays in various absorption doses which allow us to analyze anion center distribution. The example research shows that the size and element density of anion nanocenters depends on the radiation dose. The high fraction of atomic oxygen emerged on the surface of mixed nano-Al₂O₃ and Al₂O₃-CuO shows a continuing increase depending on absorption dose, while the initial radiation creates additional anion (O–) centers. Consequently, a contraction of the energy required to activate the centers derives faster conversion.     

The electronic structure of the doped one-dimensional transition metal oxide Y 2 - x Ca x BaNiO 5 studied using X-ray absorption

A strong anisotropic distribution of the holes in Ni 3 d and O 2 p orbitals is observed in the polarization dependent O 1 s and Ni 2 p _3/2 X-ray absorption spectroscopy of the linear-chain nickelate Y_2-xCa_xBaNiO₅ (x = 0, 0.05, 0.1, 0.2), which demonstrates the one-dimensional nature of the electronic state in these compounds. The holes introduced by Ca-doping occupy both O 2 p and Ni 3 d orbitals along the NiO₅ chains. By comparing the experimental Ni 2 p _3/2 absorption spectra of Y_2-xCa_xBaNiO₅ to those from charge transfer multiplet calculations we can derive the orbital character of the additional holes to be of ∼60% O2 p and ∼40% Ni 3 d. Received 7 January 2002     

Diode laser spectrum of ammonia around 16 μm

The absorption spectrum of ammonia over the range 620–634 cm^?1 has been investigated with a diode laser. Multiplets have been resolved and almost all the lines, mainly Q-branch transitions of the s2ν₂ ← aν₂ band, have been identified.     

Photofragmentation of hydrated iron ions Fe(HO) () at 532, 355 and 266 nm

Photofragmentation of Fe(H₂O)n ⁺ clusters (n =1-9) is investigated at three different wavelengths, 532, 355 and 266 nm. Two fragmentation pathways are observed depending essentially on the photon energy, but also on the parent size n. The fragmentation products belong to two ion families, Fe(H₂O)m ⁺ and FeOH(H₂O)m ⁺ , which correspond to dehydration and intracluster dehydrogenation reactions respectively. The ion yields are studied as a function of the laser fluence in order to determine the number of photons implied in the photofragmentation process. This allows us to estimate that the D[(H₂O)_n-1Fe^+-(H₂O)] bond energy is ranging between 0.44 eV and 0.55 eV for .Photon absorption cross sections are also derived from the fluence experiments, and two different behaviors are observed: i) At 355 nm, far away from any transition, progressive solvation of the metal ion results in an increasing absorption cross section from n =2 to n =9. This can be attributed to a forbidden transition of bare , which becomes progressively allowed because of the interaction with more and more water ligands. ii) At 266 nm, close to several allowed transitions of bare , a distinct maximum is observed for the absorption of ion. It may be attributed to a change in the spin multiplicity when switching from and on one hand to Fe(H₂O) on the other. Received: 11 November 1997 / Revised: 18 February 1998 / Accepted: 22 April 1998     

Ultrafast dynamics in the excited hydrogen atom transfer states of ammonia clusters

Neutral ammonia clusters (NH₃)_m are photo-excited to the electronic state by a deep UV femtosecond laser pump pulse. Within a few hundred femtoseconds a significant fraction of the clusters rearrange to form an H-transfer state (NH₃)_m-2NH₄(3s)NH₂ with the subunit NH₄ in its 3s electronic ground state. This state is then electronically excited by a time-delayed infrared control pulse of variable wavelength. Finally, a third (probe) pulse in the UV ionizes the clusters for detection. The lifetime of the excited (NH₃)_m-2NH₄(3p)NH₂ states is found to vary between 2.7 and 0.13 ps depending on cluster size and excitation energy. It increases drastically upon deuteration. The corresponding cluster size-dependent photoelectron spectra allow us to disentangle the underlying energetics of the excitation and ionization process and reveal additional processes, such as nonresonant ionization or dissociative ionization. The experimental findings suggest that the excited H-transfer ammonia complexes with m > 2 are deactivated by an internal conversion process back to the electronically lowest H-transfer state followed by fast dissociation. Received 22 September 2001 and Received in final form 31 January 2002     

High resolution laser spectroscopy of NaAr: Improved interaction potential for the ground state

The absorption spectrum of NaAr has been investigated with high resolution using a supersonic beam of molecules and a tunable dye laser. About 3 300 absorption lines due to the transition A ² Π ← X and B ² Σ ← X have been observed. In addition, we observed the spectral distribution of the fluorescence for a particular absorption line. From all experimental data the X ² Σ ⁺ interaction potential has been deduced in a fully quantum-mechanical method of approach. The potential is given in terms of an analytical Hartree-Fock-Dispersion function. For the equilibrium parameters of the X state we get R _e = 5.01(1) ? and D _e = 41.6(2) cm ^-1 . Received 28 August 2002 / Received in final form 15 October 2002 Published online 17 December 2002 RID="a" ID="a"Now at Knick Elektronische Messger?te, Beuckestr. 22, 14163 Berlin, Germany. RID="b" ID="b"e-mail: dz@kalium.physik.tu-berlin.de     

Cusp satellite bands in the spectrum of molecule

We report measurements and a theoretical explanation of the cusp-shaped satellite bands in the blue wing of the cesium D₂ resonance line which have been observed for the first time. The bands are identified as transitions where the upper state dissociates into the 6 ²P _3/2 + 6 ² S _1/2 atomic asymptote. The experiment has been performed using a standard absorption setup, computer controlled data acquisition and computer data processing. We have shown that the peculiar shape of the difference-potential curve is solely responsible for the spectrum containing the cusp-shaped satellite bands. The appearance of these satellite bands has been discussed and explained relating the theory of satellite bands to the catastrophe theory. The shape of the line wing and of the satellite bands have been calculated using the Fourier transform technique. To ensure a more stringent comparison between the experimental and the theoretical spectrum, we have analyzed and compared the derivatives of the measured and the calculated satellite band shape. On the contrary to the customary direct comparison between the measured and the calculated absorption coefficient, the derivative clearly shows all differences and resemblances between satellite band profiles. The degree of coincidence of the experimentally observed and the theoretically calculated satellite band shape can be used as an ultimate check on the assessment of the quality of potential-energy curves involved in the formation of satellite bands. Received: 1 October 1997 / Revised: 14 January 1998 / Accepted: 24 February 1998     

Computational study of linear and nonlinear optical properties of substituted thiophene imino dyes using long-range corrected hybrid DFT methods

The molecular structures, linear and nonlinear optical properties of a series constituted by four R-substituted thiophene imino dyes, namely A(R?=?SO₂Me), B(R?=?SO₂Ph), C(R?=?NO₂), and D(R?=?C₂(CN)₃) were analysed using CAM-B3LYP, ωB97XD and LC-ωPBE hybrid DFT functionals in combination of the 6-311++G(d,p) standard basis set. The dipole moments, polarisabilities, HOMO-LUMO energy gaps, maximum absorption wavelengths and first hyperpolarisabilities were calculated in the gas phase and the obtained results are in good agreement with experimental NLO activity order A?<?B?<?C. Compared to synthesised dyes A-C, the designed dye D presents a longer maximum absorption wavelength and a lower HOMO-LUMO gap because of the appreciable stabilisation of its LUMO energy. These results were confirmed by the calculation of the total second-order stabilisation energy E⁽²⁾ defined in the context of the NBO population analysis. Consequently, dye D is predicted to exhibit a higher first hyperpolarisability in comparison with dyes A-C. This result can be justified by the enhanced intramolecular charge transfer in dye D due to the stronger electron-withdrawing ability and the cumulative action of the long π-conjugation of the tricyanovinyl moiety. The very high total hyperpolarisability (27 times greater than that of para-nitroaniline) of the designed dye D suggests its promising use in organic NLO devices.     

Comparative first-principles analysis of the absorption spectra of ZnAl2S4 and ZnGa2O4 crystals doped with Cr3+

Systematic first-principles analysis of the energy level schemes and ground state absorption spectra of trivalent chromium in ZnAl₂S₄ and ZnGa₂O₄ crystals has been performed in the present paper. The recently developed first-principles approach to the analysis of the absorption spectra of impurity ions in crystals based on the discrete variational multi-electron (DV-ME) method [K. Ogasawara et al., Phys. Rev. B 64, 115413 (2001)] was used in the calculations. The method is based on the numerical solution of the Dirac equation; no phenomenological parameters are used in the calculations. As a result, complete energy level schemes of the Cr³⁺ ion and its absorption spectra in both crystals were calculated, assigned and compared with experimental data. By performing analysis of the molecular orbital (MO) population, it was shown that the covalency of the chemical bonds between the Cr³⁺ and S^2- ions is more significant than that one between the Cr³⁺ and O^2- ions.     

3D Flake‐Like Bi2Te3 with Outstanding Lightweight Electromagnetic Wave Absorption Feature

Flake‐like semiconductors with strong interfacial polarization exhibit excellent electromagnetic absorption properties. To the best of the knowledge, 3D flake‐like Bi₂Te₃ is never reported as effective MAMs (microwave absorption materials). Herein, it is first introduced the novel lightweight microwave absorption of 3D flake‐like Bi₂Te₃ synthesized by a simple hydrothermal process. Compared with the traditional research objects, the obtained Bi₂Te₃ possessed prominent absorbing ability at a rather thin thickness (1.0 mm), which will draw much attention to new‐materials for electromagnetic wave absorption.     

X-ray spectroscopic study of zirconium and molybdenum diselenides

The K absorption spectra of zirconium, molybdenum and selenium in ZrSe₂ and MoSe₂ have been recorded photographically using a Cauchois type bent crystal (mica) spectrograph. The absorption edge shifts are used along with the data for NbSe₂ (Bhide and Bahl 1971J. Phys. Chem. Solids 32 1001) to propose bond schemes for these compounds.     

Energy absorption buildup factors of some potential bioactive compounds in the energy region 0.015–15 MeV

Kinetic energy released per unit mass relative to air and energy absorption buildup factors has been calculated for some potential bioactive compounds in the energy region of 0.015–15?MeV. The bioactive compounds of 1-aryl-3-dibenzylamino-propane-1-on hydrochloride type Mannich bases were used in this work. Aryl part was changed as C₆H₅ (1), 4-CH₃C₆H₄ (2), C₄H₃S-2-yl (3), 4-FC₆H₄ (4), 4-BrC₆H₄ (5), 4-ClC₆H₄ (6), and 4-NO₂C₆H₄ (7). The energy absorption buildup factors have been calculated for penetration depth of 40 mean free paths. It is observed that kinetic energy released per unit mass relative to air depends on the photon energy and chemical content of compounds. The compounds with least mean atomic number possess the maximum value of energy absorption buildup factors. Also, the energy absorption buildup factors are found the highest in intermediate energy, whereas the lowest in low as well as high energies.     

Inline multi-harmonic calibration method for open-path atmospheric ammonia measurements

We demonstrate a real-time inline calibration method for an open-path ammonia sensor using a quantum cascade laser (QCL) at 9.06 μm. Ethylene (C₂H₄) has an absorption feature partially offset from the ammonia absorption feature, and the ethylene signal serves as a reference signal for ammonia concentration in real time. Spectroscopic parameters of ammonia and ethylene are measured and compared with the HITRAN database to ensure the accuracy of the calibration. Multiple harmonic wavelength modulation spectroscopy (WMS) signals are used to separate the ambient ammonia and reference ethylene absorption signals. The ammonia signal is detected with the second harmonic (2f), while it is calibrated simultaneously with a high-harmonic (6–12f) signal of ethylene. The interference of ambient ammonia absorption on the ethylene reference signal is shown to be negligible when using ultra high-harmonics (≥6f). This in situ calibration method yields a field precision of 3 % and accuracy of 20 % for open-path atmospheric ammonia measurements.     

Temperature dependence of oxygen content and phase transition in Y1Ba2Cu3O9−x compounds

Systematic TGA (Thermogravimetric analysis), magnetic susceptibility measurements and X-ray diffraction investigations have been made on the temperature dependence of oxygen content and phase transition in Y₁Ba₂Cu₃O_9–x compounds. The experimental results show that reversible oxygen relief and absorption appeared during heating and cooling in the temperature range of 400–950°C. A low cooling rate leads to higher oxygen content and quenching can suppress oxygen absorption. The deoxidation process is accompanied by a change of the cell constants,a andb increase whilec decreases with reduced oxygen content while the phase transition from the ortorhombic to the tetragonal system appeares. Nevertheless, this transition is a gradually changing process, no critical point of transition exists. Quenching stress and defects have a pronounced influence on the absorption and relief of oxygen. Maximum rates of oxygen relief and absorption were obtained at about 650°C. Oxygen absorption and desorption can be obtained only in an athermal process. Magnetic susceptibility measurements show that diamagnetic and paramagnetic suceptibilities increase obviously with increasing oxygen content. Deoxidation and oxygen absorption can be restrained by adding Fe to the Y₁Ba₂Cu₃O_9–x phase, which suggests that deoxidation and oxygen absorption are very sensitive to crystal structure and lattice distortions.     

Pressure broadening spectroscopy of formaldehyde,ammonia, isocyanic acid,trimethylene sulfide,and methyl chloride using far-infrared lasers

Pressure-broadened rotational spectra were observed for H₂CO, NH₃, HNCO, CH₃Cl, and CD₃Cl in the far-infrared region using the H₂O, D₂O, and HCN lasers. Absorption due to a ring-puckering transition was also observed for (CH₂)₃S. In cases where the absorption lines are well isolated from other lines, we could determine two parameters from the pressure dependence of the absorption coefficient at the laser frequency, that is, the peak absorption coefficient α₀ and the separation between the transition and laser frequency divided by the pressure broadening parameter γ = |ν - ν_L|/Δν_p. Molecular constants obtained from other sources are used to estimate |ν - ν_L| and Δν_p separately. The dependence of the pressure broadening parameter on the rotational quantum numbers J and K is discussed for ammonia and methyl chloride.     

Effect of bridging aza-substitution on electronic structure and spectral-luminescent properties of isobacteriochlorin NH-isomers

We have investigated the spectral characteristics, quantum yield ϕ_F, lifetime τ_F, and polarization of fluorescence of NH-isomers of dibenzobarrelene disubstituted tetraazaisobacteriochlorin at 293 and 77 K. The following information has been obtained from low-temperature measurements: 1) the weak shoulder on the edge of the long-wavelength 0-0 absorption band disappears at 77 K and, therefore, can be assigned to the cis-NH-isomer [the principal component of the tautomeric mixture is the trans-isomer a (b)]; 2) the low value of ϕ_F at room temperature is due to temperature-viscosity quenching whereas ϕ_F at 77 K is close to 1 and τ_F = 5.3 nsec; 3) the energy of the weak electronic transition G → Q₂ and the interval have been determined. Quantum-chemical calculations found that replacing the methine bridges by nitrogen stabilizes the non-aromatic trans-isomer a (b) whereas the non-planarity of the macrocycle and the alternation of bond lengths increase for the cis-isomers. The calculated electronic absorption spectra of the a isomer reproduce rather well the experimental data. It is shown that the four-orbital model is applicable for the lower excited states Q₁ and Q₂ for all NH-isomers. __________ Translated from Zhurnal Prikladnoi Spektroskopii Vol. 74, No. 3, pp. 395–407, May–June, 2007.     

Wavelength modulated cavity enhanced absorption spectroscopy of ammonia at 1994 nm

We describe the sensitive detection of ammonia by wavelength modulated cavity enhanced infrared tunable diode laser absorption spectroscopy at 1994 nm. The spectrometer can measure a fractional absorption of ∼10^-5 for an absorption pathlength of a few kilometers. The spectral resolution and sensitivity are sufficient to measure ammonia isotopomers (¹⁴NH₃, ¹⁵NH₃) in planetary atmospheres. The spectrometer is miniaturisable, so a future multiple-species version will be highly suitable for in situ planetary exploration and life-detection. PACS 42.62.Fi; 33.20.-t; 33.20.Ea