UV-VUV absorption spectra of azido-based energetic plasticizer bis(1,3-diazido prop-2-yl)malonate in gas phase.

Ultraviolet and vacuum ultraviolet photo-absorption spectra of azido (-N3)-based energetic plasticizer, bis(1,3-diazido-prop-2-yl)-malonate (abbreviated as BDAzPM), in the gas phase is recorded at room temperature and in the photon energy range of 5.5-9.9 eV using a synchrotron radiation source. Complementary computational results obtained using the time-dependent density functional theory document the vertical transition energies and oscillator strengths. Comparison of the simulated spectra with the experimental absorption spectrum of BDAzPM reveals that the early part of the absorption spectrum of BDAzPM is of pure valence excitation character, whereas the later intense part of the absorption spectrum is dominated by mixed Rydberg and valence electronic excitations.

Elemental analysis of residual ash generated during plasma incineration of cellulosic, rubber and plastic waste.

Management of plastic, rubber and cellulosic waste from various industries is a challenging task. An engineering scale plasma pyrolysis based incinerator has been commissioned for incineration of combustible waste, including plastic, rubber and cellulose. Operational trials of wastes with simulated composition show a weight reduction factor of more than 18 and volume reduction factor of more than 30. The volume reduction factor is tenfold higher than the compaction process currently practised for rubber and plastic wastes. Representative residual ash samples derived from these runs are subjected to their elemental analysis using EDXRF technique and results are comparable with the published literature. Relative variation of individual elements is attributed to the type of waste and feed composition. Analysis is aided with the calculation of index of geoaccumulation, enrichment factor (EF), contamination factor (CF) and pollution load index (PLI). From this study, it is evident that S, Cr, Zn, As, Se, Hg and Pb are of concern for environment in residual ash from plasma incineration of combustible waste. The efficacy of the incineration process is evaluated; C, H and O reduction achieved is more than 98% and overall enrichment ratio (ER) for the inorganic elements is more than 4.5. This study highlights the importance of elemental composition for the performance analysis of the plasma based incineration as well as hazards evaluation of constituents in residual ash for its further management.

Development of an experimental set-up for low-temperature spectroscopic studies of matrix-isolated molecules and molecular ices using synchrotron radiation.

An experimental set-up for studying photophysics and photochemistry of molecules in an inert gas medium (matrix-isolated) and in the ice phase at low temperatures has been developed and commissioned at the Photophysics beamline, Indus-1 synchrotron radiation source. This end-station uses an in-house-developed closed-cycle cryostat for achieving cryo-temperatures (∼10 K). Synchrotron radiation from the Photophysics beamline is used as the source of UV-VUV photons and the system is equipped with a Fourier transform infrared spectrometer for characterization of the molecular species formed at low temperature. Various individual components of the end-station like closed-cycle cryostat, experimental chamber, gas mixing and deposition systems are tested to ascertain that the desired performance criteria are satisfied. The performance of the composite system after integration with the Photophysics beamline is evaluated by recording IR and UV-VUV photoabsorption spectra of sulfur dioxide at low temperatures (10 K), both in the ice phase as well as isolated in argon matrices. Results obtained are in good agreement with earlier literature, thus validating the satisfactory performance of the system. As an off-shoot of the study, the VUV absorption spectrum of matrix-isolated SO2 in argon matrix up to 10.2 eV is reported here for the first time. This experimental end-station will provide new opportunities to study photon-induced reactions in molecules of environmental, astrochemical and industrial importance. Details of the design, development and initial experimental results obtained are presented.

Electronic spectroscopy of ethyl bromide probed by VUV photoabsorption and quantum chemical calculations.

The electronically excited states of ethyl bromide and its deuterated isotopologue (C2H5Br and C2D5Br) are studied using synchrotron radiation based photoabsorption spectroscopy in the wavenumber region 50 000-86 000 cm-1. A detailed spectral analysis supported by quantum chemical calculations is presented. A complex Rydberg series structure comprising of nsa1, npa1, npe, nda1 and nde series, converging to each of the two spin-orbit split components of the first ionization potential (2E3/2 and 2E1/2) is observed for both the isotopologues. Quantum defect values are consistent with excitation from Br lone pair orbitals. Rydberg series analysis is extended to several higher members as compared to earlier work and corroborates the dominance of the spin-orbit mechanism over the hyperconjugative effect. A few new Rydberg series members converging to the second and third ionization potentials are observed and assigned. The complete gas phase VUV photoabsorption spectrum of C2D5Br up to its first ionization limit and its infrared absorption spectrum in the liquid phase are reported for the first time. An extended vibronic analysis of bands accompanying the first few Rydberg series is reported along with several new assignments. DFT calculations on ground states of neutral and ionic species and TDDFT calculations on singlet and triplet excited states aid and support the spectral analysis. Potential energy curves with respect to the C-Br bond length and the C-C-Br bond angle provide further insights into the nature of the excited states. This work represents a comprehensive study of the electronic absorption spectrum of ethyl bromide and its deuterated counterpart.

Spectroscopy of N,N-dimethylformamide in the VUV and IR regions: Experimental and computational studies.

The electronic absorption spectrum of N,N-dimethylformamide (DMF) is studied in the 45 000-80 000 cm-1 (5.6-9.9 eV) region using synchrotron radiation. The vacuum ultraviolet (VUV) spectrum comprises mostly of Rydberg series of ns, np, and nd types converging to the first two ionization potentials (IPs). Quantum defect values obtained are consistent with excitation of an electron from the highest occupied molecular orbitals localized on nitrogen (4a″) and oxygen (16a'); in addition, the 3s Rydberg transition converging to the third IP (3a″) is observed at 8.95 eV. A reinvestigation of the infrared spectrum of DMF in the 500-4000 cm-1 region with the help of density functional theory (DFT) calculations establishes the planarity of the ground state and leads to revision of several vibrational assignments. Vertical excited state energies and their valence/Rydberg character are predicted using time dependent DFT calculations; excellent correlation is achieved between theoretical results and experimentally observed spectral features. Potential energy curves of the first few excited states give additional insights into the nature of the excited states and their role in photodissociation dynamics. The absorption spectrum of DMF in the region >63 400 cm-1 (7.85 eV) as well as a complete set of spectral assignments in the VUV region (45 000-80 000 cm-1) is reported for the first time. This work represents a comprehensive study of the absorption spectra of DMF in the VUV and infrared regions.

Electronic state spectroscopy of diiodomethane (CH2I2): experimental and computational studies in the 30,000-95,000 cm⁻¹ region.

The electronic absorption spectrum of diiodomethane in the 30,000-95,000 cm(-1) region is investigated using synchrotron radiation; the spectrum in the 50,000-66,500 cm(-1) region is reported for the first time. The absorption bands in the 30,000-50,000 cm(-1) region are attributed to valence transitions, while the vacuum ultraviolet (VUV) spectrum (50,000-95,000 cm(-1)) is dominated by several Rydberg series converging to the first four ionization potentials of CH2I2 at 9.46, 9.76, 10.21, and 10.56 eV corresponding to the removal of an electron from the outermost 3b2, 2b1, 1a2, and 4a1 non-bonding orbitals, respectively. Rydberg series of ns, np, and nd type converging to each of the four ionization potentials are assigned based on a quantum defect analysis. Time dependent density functional theory calculations of excited states support the analysis and help in interpretation of the Rydberg and valence nature of observed transitions. Density functional theory calculations of the neutral and ionic ground state geometries and vibrational frequencies are used to assign the observed vibronic structure. Vibronic features accompanying the Rydberg series are mainly due to excitation of the C-I symmetric stretch (ν3) and CH2 wag (ν8) modes, with smaller contributions from the C-H symmetric stretch (ν1). UV absorption bands are assigned to low lying valence states 1(1)B2, 1(1)B1, 2(1)A1, 3(1)A1, 2(1)B1, and 2(1)B2 and the unusually high underlying intensity in parts of the VUV spectrum is attributed to valence states with high oscillator strength. This is the first report of a comprehensive Rydberg series and vibronic analysis of the VUV absorption spectrum of CH2I2 in the 50,000-85,000 cm(-1) region. The VUV absorption spectrum of CD2I2 which serves to verify and consolidate spectral assignments is also reported here for the first time.

Multiplet splittings and intensities of fine structure components of the Q1(0)H2 + S0(0)N2 transition in a solid parahydrogen matrix.

A comprehensive analysis of theoretical multiplet splittings and intensities of the fine structure components of the Q(1)(0)H(2) + S(0)(0)N(2) transition in a solid parahydrogen crystal is presented. The consideration of higher order anisotropic term responsible for splittings is essential to explain the observed splitting of the three components. The pair interaction parameters DeltaB and DeltaC have been determined by comparing the theoretical splittings with the experimental values. The information about the small splittings (approximately 0.1 cm(-1)) due to crystal-field interaction is completely obscured due to fast hopping of v(') = 1, J(') = 0 H(2) vibron. Also, the theoretical expressions are derived for the intensities of the fine structure components of the Q(v(H(2)))(0) + S(v(N(2)))(0) transition and the theoretical results are compared with the experimental findings.