The 280-nm absorption system of benzoyl fluoride

Benzoyl fluoride exhibits a weak, discrete absorption system in the region 290 – 260 nm. Vibrational structure associated with the C₆H₅COF and C₆D₅COF isotopes has been analyzed in detail. The C₆H₅COF and C₆D₅COF origin bands lie at 35 685 and 35 829 cm^?1, respectively. The intensity in the spectrum is principally associated with two progressions, ν′₁₉, the breathing vibration of the benzene ring and ν′₂₄, a COF in-plane bend, and sequence bands involving the COF torsion motion ν₃₆. The $\text{C}{}_6\text{H}{}_5\text{COF}\text{C}{}_6\text{D}{}_5\text{COF}$ν₁₉, ν₂₄, and ν₃₆ vibrational frequencies are respectively 1005/-, $\text{376}\text{357}\text{,}\text{and}\text{57}\text{55}\text{cm}{}^{\mathrm{?1}}$ in the ground state and $\text{950}\text{919}\text{,}\text{348}\text{331}\text{,}\text{and}\text{89}\text{85}\text{cm}{}^{\mathrm{?1}}$ in the excited state. The barriers to rotation of the COF group are estimated from the torsional frequency data to be 1450 and 3450 cm^?1 in the ground and excited electronic states, respectively.     

The 275-nm absorption system of anisole

The 275-nm absorption systems of anisole (methoxybenzene) and three deuterated derivatives have been photographed at medium to high resolution. The origin bands lie at 36 386.4, 36 389.6, 36 557.2, and 36 560.4 cm^?1 for C₆H₅OCH₃, C₆H₅OCD₃, C₆D₅OCH₃, and C₆D₅OCD₃. The vibrational structure, which was analyzed in some detail, was found to be very similar to that of the analogous system of phenol. The spectrum consists of both allowed and forbidden components although the forbidden component, principally evident through activity of vibrations 18b and 6b, is relatively weak.     

The microwave spectrum,structure, and dipole moment of propiolyl fluoride

The microwave spectrum of propiolyl fluoride has been observed in the frequency region 12.5–40 GHz. Rotational transitions have been assigned for the ground and two excited vibrational states of the normal isotopic species and for the ground vibrational state of the deuterated species. In each case, values for the rotational constants and centrifugal distortion constants have been obtained. The molecule has been shown to be planar and structural calculations suggest no anomalies in any of the internuclear parameters. Stark effect measurements have yielded a value of 2.98 ± 0.02 Debyes for the dipole moment.     

Selenium dioxide: Analysis of the 419-nm absorption system

The C absorption systems in the region 370–500 nm of the three isotopic species ⁷⁸Se¹⁶O₂, ⁸⁰Se¹⁶O₂, and ⁷⁸Se¹⁸O₂ have been comparatively studied in the vapor phase. The 0₀⁰ band is at 23840, 23840, and 23842 cm^?1, respectively. The vibrational structure consists of long progressions in the bending mode ν′₂(a₁) ～ 200 cm^?1, which are based on the origin band and on vibronic origins in which all three normal modes can be active. Most bands are severely overlapped, so that detailed rotational analyses are not possible. Band contour analysis of the 2₀²3₁⁰ band indicates that the transition is ${}^3\text{B}{}_2\text{-}\text{X}\text{?}{}^1\text{A}{}_1$, which acquires intensity by both spin-orbit and spin-vibronic coupling mechanisms. The estimated bond length and angle in the triplet state are 1.69 Å and 100°, respectively, the latter representing a large decrease from the ground state value of 114°.     

276-nm absorption band system of m-dichlorobenzene: Vibrational fine structure analysis

The vibrational fine structure accompanying the 276-nm absorption band system (${}^1\text{B}{}_2\text{←}{}^1\text{A}{}_1$) of m-dichlorobenzene (m-DCB) vapor has been reanalyzed. Unambiguous assignments for about 80% of the measured transitions have been presented here. The assignments have been greatly facilitated by the results of band contour analysis as well as Raman and ir data. Vibrational fine structure assignments have led to a determination of excited state fundamentals which are not allowed to appear in single quantum excitation. Wherever possible, a close correspondence has been established between the various normal modes of m-DCB and benzene.     

276-nm absorption band system of m-dichlorobenzene: Rotational band contour analysis

The 276-nm absorption band system (${}^1\text{B}{}_2\text{←}{}^1\text{A}{}_1$) of m-dichlorobenzene was photographed under high resolution. The electronic origin band (0, 0) and a band at (0 + 380) cm^?1 were subjected to rotational “band contour” analysis. As a result, it is found that the origin band has a type A band contour and that at (0 + 380) cm^?1 exhibits a type B band contour. The band contour analysis also yields an accurate determination of the excited state parameters, viz., A′ = 0.0911 ± 0.0003, B′ = 0.02852 ± 0.00005, and C′ = 0.02175 ± 0.00001 cm^?1. A model geometry for the molecule m-DCB in its first excited singlet state has been proposed.     

The 404.5-nm system of the ReO molecule

Observations on the emission spectrum of ReO in the region 375–870 nm are reported. Five bands of a $\text{ΔΩ}\text{= 0}$ system with (0, 0) band at 404.5 nm have been rotationally analyzed and the principal results for ¹⁸⁷ReO are (in cm^?1) ν₀ = 24 709.90, B′_e = 0.3819, B″_e = 0.4252, ω′_e = 874.8₂, and $\text{Δ}\text{G″(}\text{1}\text{2}\text{) = 979.1}{}_2$. Data on the minor isotopic species ¹⁸⁵ReO are also reported. It is suggested that broad rotational profiles found in bands near 842 nm may be due to nuclear hyperfine structure.     

Excimer-laser-induced degradation of fused silica and calcium fluoride for 193-nm lithographic applications

We report the initial results of a large-scale evaluation of production-grade fused silica and calcium fluoride to be used in 193-nm lithographic applications. The samples have been provided by many different suppliers of materials. A marathon irradiation chamber permits simultaneous exposure of as many as 36 samples at 800 Hz, at fluences from 0.2 to >/=4 (mJ/cm(2))/pulse and pulse counts in excess of 10(9) . The initial absorption and the laser-induced absorption are found to vary over a wide range. The compaction of each fused-silica sample follows a power law, but its parameters can differ widely from sample to sample.     

784-nm amplified spontaneous emission from Tm3+-doped fluoride glass fiber pumped by an 1120-nm fiber laser

We report 784-nm (1G4 --> 3H5 transition) amplified spontaneous emission (ASE) from Tm3+-doped fluoride (ZrF4-BaF2-LaF3-AlF3-NaF) glass fiber pumped by an 1120-nm fiber laser. To our best knowledge, this is the first report of 784-nm (1G4 --> 3H5 transition) ASE in a Tm3+-doped fluoride fiber laser. Its effects on a 480-nm (1G4 --> 3H6 transition) blue laser were also discussed.     

Intracavity laser absorption spectroscopy of platinum fluoride, PtF

Two vibrational bands of an electronic transition of PtF occurring at 11 940 cm⁻¹ and 12 496 cm⁻¹ were recorded and analyzed. These transitions are identified as the (0,0) and (1,0) bands of an [11.9] Ω = 3/2 − XΩ = 3/2 electronic transition. Gas phase PtF was produced in a copper hollow cathode lined with platinum foil using a trace amount of SF₆, and the spectrum was recorded at Doppler resolution by intracavity laser absorption spectroscopy. This work represents the first published spectroscopic data on PtF. Molecular constants for the ground and excited electronic states are presented.     

Spectral-kinetic characteristics of transient absorption in calcium fluoride crystals

The method of absorption spectroscopy with nanosecond resolution is used to study transient absorption in nominally pure crystals of CaF₂ irradiated by a pulse of fast electrons. Optical absorption caused by self-trapped excitons appears in the form of a superposition of bands with half-widths of no more than 0.2 eV in both the electron and hole components. These groups of bands are assigned to absorption of F, H pairs in various configurations. We observe a regular change in the spectral-kinetic characteristics depending on the distance between the components of the pair. Fiz. Tverd. Tela (St. Petersburg) 39, 1197–1201 (July 1997)     

The 2780 Å absorption system of thiophosgene

The vapor phase absorption spectrum of thiophosgene (Cl₂CS) in the 2500–2900 Å region consists of a broad intense band ($\text{log}\text{?}{}_{\mathrm{<mtext>max</mtext>}}\text{= 3.5}\text{at}\text{2540}\text{A}\text{?}$. On the red side of this a vibrationally discrete structure is found which becomes increasingly diffuse and merges into the broad band as the wavelength is decreased. It is shown that this vibrational structure can be explained as due to a $\text{π → π}{}^1$, ${}^1\text{A}{}_1\text{-}\text{X}\text{?}{}^1\text{A}{}_1$ electronic transition between a planar ground state and a pyramidal excited state of the molecule. In the latter state, the CS stretching mode ν₁′(a₁) = 681 cm^?1 and the CCl bending mode ν₃′(a₁) = 147 cm^?1. From the inversion doublet splitting of the out-of-plane mode ν₄′(b₁), the barrier to inversion is calculated to be ～126 cm^?1, with an equilibrium out-of-plane angle of ～20°.     

Excited state absorption spectroscopy for thulium-doped zirconium fluoride fiber

The excited state absorption (ESA) transitions at 1050 and 1420 nm play a fundamental role in thulium-doped fiber amplifiers (TDFA). We present a novel setup to measure the spectral cross-sections of these transitions in amplifier fibers and the results of this measurement in case of thulium-doped fluorozirconate (ZBLAN) fibers. Besides a standard system for fiber attenuation measurements and a long-pass filter, we use only components from the fiber amplifier setup, including the active fiber. No special parts are needed. We show that this fiber optic method delivers reliable results for different lengths of the doped fibers. The oscillator strengths of the measured transitions are calculated and compared to values published in the literature.     

The 341-nm band system of pyridine N-oxide: Assignment of the out-of-plane fundamentals

Analysis of the 341-nm bands of pyridine N-oxide vapor has been extended to the out-of-plane modes of the molecule in the $\text{X}\text{?}{}^1\text{A}{}_1$ and $\text{A}\text{?}{}^1\text{B}{}_2$ states. Data for the ground state are obtained primarily from infrared and Raman measurements; using this information, the excited-state out-of-plane manifold is then built up by the assignment of overtone, sequence, and cross-sequence bands observed in the electronic absorption spectrum. These assignments lead to a complete set of a₂ and b₁ fundamental frequencies in the $\text{A}\text{?}$ and $\text{X}\text{?}$ states, though some questions cannot be fully resolved, and the uniqueness of the assignments is briefly discussed.     

Vacuum ultraviolet absorption of lithium fluoride crystals grown by zone melting

Optical properties are reported for LiF crystals obtained by zone melting from salts differing in synthesis and purity. The impurity distributions along the bars have been studied by chemical analysis and absorption spectrometry. The transparency is discussed as a function of the number of zone passes.