Absorption Spectrum of HSiI

1972 ◽  
Vol 50 (6) ◽  
pp. 531-543 ◽  
Author(s):  
J. Billingsley
Keyword(s):  
Absorption Spectrum ◽  
Electronic State ◽  
Isotope Shift ◽  
Flash Photolysis ◽  
Bond Angle ◽  
Rotational Analysis ◽  
Lower Electronic State ◽  
Deuterium Isotope Shift ◽  
Axis Switching

A new absorption spectrum in the region 4600–5600 Å has been discovered in the flash photolysis of silyl iodide, SiH3I. A rotational analysis, together with the observation of a deuterium isotope shift, has shown that the spectrum is due to the HSiI radical.The lower electronic state of HSiI is a 1A′ state with a bond angle of ~103°, and the upper state is 1A″ with angle ~116°. Axis-switching effects, due to the increase in bond angle, cause the appearance of ΔK = 0, ± 2 subbands, in addition to the ordinary ΔK = ± 1 subbands.

THE SPECTRUM AND STRUCTURE OF THE HNO MOLECULE

1958 ◽  
Vol 36 (10) ◽  
pp. 1336-1371 ◽  
Author(s):  
F. W. Dalby
Keyword(s):  
Nitric Oxide ◽  
Absorption Spectrum ◽  
Electronic State ◽  
Flash Photolysis ◽  
Molecular Geometry ◽  
Rotational Analysis ◽  
Experimental Conditions ◽  
Long Wavelength ◽  
Lower Electronic State ◽  
State Formula

The absorption spectrum of HNO in the region 6500–7700 Å has been photographed on a 35-ft grating. The observed spectrum consists of three bands: an intense one at the long-wavelength end of the spectrum and two weaker bands towards shorter wavelengths. All the bands have extensive rotational structure of the perpendicular type. The spectrum was observed after the flash photolysis of nitromethane, nitroethane, isoamyl nitrite, and mixtures of nitric oxide and ammonia. The "lifetime" of the HNO was about 1/10 second under our experimental conditions. The spectrum of DNO has also been photographed. From the constants obtained from the rotational analysis the molecular geometry has been determined. For the lower electronic state[Formula: see text]For the upper electronic state[Formula: see text]The most probable identification of the observed electronic transition is 1A″ ← 1A′.

ROTATIONAL ANALYSIS OF BANDS OF THE HCF MOLECULE

1966 ◽  
Vol 44 (7) ◽  
pp. 1541-1550 ◽  
Author(s):  
A. J. Merer ◽  
D. N. Travis
Keyword(s):  
Transient Absorption ◽  
Flash Photolysis ◽  
Bond Angle ◽  
Large Change ◽  
Transient Absorption Spectrum ◽  
Rotational Analysis ◽  
Molecular Constants ◽  
Ordinary Type ◽  
Type C ◽  
Axis Switching

A new transient absorption spectrum, belonging to the HCF free radical, has been discovered in the flash photolysis of dibromofluoromethane, HCFBr2. The spectrum consists of a single progression of complex bands in the region 4 300–6 000 Å. Rotational analysis of the less severely perturbed bands shows them to be type-C bands of a molecule that is nonlinear in both upper and lower states of the transition, with bond angles of ~ 127° and ~ 102° respectively. Axis-switching effects, due to the large change of bond angle in the transition, cause the appearance of prominent gQ, qQ, and °Q branches, in addition to those obeying the ordinary type-C selection rules.The principal molecular constants of HCF (in cm−1) are:[Formula: see text]

The ultraviolet absorption spectrum of the F 2 CN radical

1967 ◽  
Vol 300 (1462) ◽  
pp. 405-414 ◽  
Keyword(s):  
Molecular Structure ◽  
Absorption Spectrum ◽  
Ground State ◽  
Flash Photolysis ◽  
Ultraviolet Absorption ◽  
Ultraviolet Absorption Spectrum ◽  
Rotational Analysis ◽  
Absorption Bands ◽  
New System

A new system of absorption bands near 3600 Å has been observed during the flash photolysis of CF 3 NCF 2 and is ascribed to the free F 2 CN radical. The rotational analysis of the 0–0 band leads to the ground state molecular structure r CF = 1.310 Å (assumed), r CN = 1.265 ± 0.02 Å, FCF angle = 113.5 + 1°. The bands are shown to be type A bands arising from the transition 2 A 1 ← 2 B 2 , and the spectrum is compared with those of the iso-electronic molecules NO 3 and F 2 BO.

THE ABSORPTION SPECTRUM OF CNC

1966 ◽  
Vol 44 (2) ◽  
pp. 353-372 ◽  
Author(s):  
A. J. Merer ◽  
D. N. Travis
Keyword(s):  
Absorption Spectrum ◽  
Bond Length ◽  
Ground State ◽  
Flash Photolysis ◽  
Electronic States ◽  
Electronic Transitions ◽  
Ultraviolet Absorption Spectrum ◽  
Rotational Analysis ◽  
Bending Vibrations ◽  
Show Evidence

The ultraviolet absorption spectrum of the free CNC radical has been discovered in the flash photolysis of diazoacetonitrile, HC(CN)N2. The identity of the radical has been proved from isotopic evidence, using 15N and 13C, together with rotational analysis of the bands. Rotational analyses have shown that the bands of CNC must be assigned to two electronic transitions, A2Δu–X 2Πg, and [Formula: see text]. The sequence bands in the bending vibrations, which are observed in both electronic transitions, show evidence of Renner–Teller interaction in both the degenerate electronic states: this interaction is extremely large in the X2Πg state. The principal constants (in cm−1) of the observed states of CNC are as follows:[Formula: see text]The C—N bond length in the ground state of CNC is found to be 1.245 Å.CNC is isomeric with CCN, whose spectrum has been reported previously; some interesting comparisons are made between the spectra of these two molecules.

Spectrum of SO: Analysis of the B3Σ−–X3Σ− and A3 Π–X3Σ− band systems

1969 ◽  
Vol 47 (9) ◽  
pp. 979-994 ◽  
Author(s):  
R. Colin
Keyword(s):  
Absorption Spectrum ◽  
High Resolution ◽  
Microwave Discharge ◽  
Flash Photolysis ◽  
Band System ◽  
Rotational Analysis ◽  
Rotational Constants ◽  
Π State

The absorption spectrum of SO radicals produced by flash photolysis of a mixture of COS + O2 + Ar is investigated. A partial rotational analysis of the previously known bands of the B3Σ−–X3Σ− transition which lie in the region of 1900 to 2400 Å is presented, and the predissociations and perturbations of the B3Σ−state are discussed. A complex red-degraded band system near 2500 Å, previously observed in emission and attributed to SO2, is shown to be due to a 3Π–X3Σ− transition of the SO molecule. Effective rotational constants of the 3Π state are derived from the analysis of these bands photographed at high resolution. In order to obtain the vibrational numbering of the 3Π–X3Σ− bands, these were also photographed in emission from a microwave discharge through a mixture of S18O2 + S16O2. A general discussion of the currently known states of the SO molecule is given.

The Absorption Spectrum of Isotopic Diatomic Antimony ( 123Sb-123Sb). Analysis of the D ← X System in the 2860—2920 Å Region

1976 ◽  
Vol 31 (2) ◽  
pp. 145-157 ◽  
Author(s):  
Abdel Mooti Sibai ◽  
Ari Topouzkhanian ◽  
Pierre Perdigon
Keyword(s):  
Absorption Spectrum ◽  
Electronic State ◽  
Rotational Constant ◽  
Rotational Analysis ◽  
Vibrational Levels ◽  
X State

Abstract A rotational analysis of several bands of the D←X system of 123Sb−123Sb is carried out. It is shown that the hitherto assumed vibrational classification of the D←X system is certainly incorrect, as well as a previously given value for the rotational constant of the X state. B(X1∑g+, ν=0) is found equal to 0.044263 cm-1. The perturbations appearing in the various vibrational levels are interpreted in terms of interactions with a new electronic state, labelled L.

The absorption spectrum of the free SiH2 radical

1968 ◽  
Vol 46 (22) ◽  
pp. 2485-2490 ◽  
Author(s):  
I. Dubois
Keyword(s):  
Absorption Spectrum ◽  
Electronic State ◽  
Vibrational Level ◽  
Visible Region ◽  
Rotational Structure ◽  
Lower State ◽  
High Dispersion ◽  
Bending Vibration ◽  
Lower Electronic State

The absorption spectrum of SiH2 in the visible region has been photographed at high dispersion and the rotational structure of three bands has been analyzed. In the lower electronic state 1A1 the HSiH angle is 92° 5′ and the Si–H distance 1.516 Å, while in the upper state these parameters are 123° and 1.487 Å, respectively. The observed bands correspond to excitation of the bending vibration [Formula: see text] in the upper state. In the lower state, only one excited vibrational level, 010, has been observed, yielding [Formula: see text].

The electronic spectra of phenyl radicals

1965 ◽  
Vol 287 (1411) ◽  
pp. 457-470 ◽  
Keyword(s):  
Absorption Spectrum ◽  
Electronic Absorption Spectrum ◽  
Electronic Absorption ◽  
Ground State ◽  
Electronic Spectra ◽  
Flash Photolysis ◽  
Visible Region ◽  
Electronic Configuration ◽  
Vibrational Structure ◽  
Fundamental Frequencies

An electronic absorption spectrum, attributed to phenyl, has been observed in the visible region with origin at 18 908 cm -1 after flash photolysis of benzene and halogenobenzenes. Similar spectra of fluoro, chloro and bromo phenyl are observed after flash photolysis of disubstituted benzenes. The vibrational structure of the phenyl spectrum has been analysed in terms of two fundamental frequencies at 571 and 896 cm -1 which correspond to the e 2 g and a 1 g frequencies of the B 2 u state of benzene. The ground state of phenyl has a π 6 n electronic configuration and the observed transition is interpreted as 2 A 1 → 2 B 1 resulting from a π → n excitation.

The absorption spectrum of SO and the flash photolysis of sulphur dioxide and sulphur trioxide

1959 ◽  
Vol 249 (1259) ◽  
pp. 498-512 ◽  
Keyword(s):  
Absorption Spectrum ◽  
Dissociation Energy ◽  
Sulphur Dioxide ◽  
Flash Photolysis ◽  
Ultra Violet ◽  
Vibrationally Excited ◽  
A Value ◽  
Continuous Absorption ◽  
Sulphur Trioxide ◽  
Normal Spectrum

The flash photolysis of sulphur dioxide under adiabatic conditions results in the complete temporary disappearance of its spectrum , which then slowly regains its original intensity over a period of several milliseconds. Simultaneously with the disappearance of the sulphur dioxide spectrum a continuous absorption appears in the far ultra-violet and fades slowly as the sulphur dioxide reappears. It is shown that the effect of the flash is thermal rather than photochemical, and the possibility of the existence of an isomer of sulphur dioxide at high temperatures is discussed; the disappearance of the normal spectrum on flashing is explained in this way. Several previously unrecorded bands of SO observed in the photolysis indicate that the vibrational numbering of its spectrum should be revised by the addition of 2 to the present values of v' . This leads to a value of the dissociation energy of 123.5 kcal. In formation about the levels v' = 4, 5 and 6 has also been obtained. The isothermal flash photolysis of sulphur trioxide results in the appearance of vibrationally excited SO, and the primary photochemical step in this reaction is discussed.

THE ABSORPTION SPECTRUM OF CF2

1967 ◽  
Vol 45 (7) ◽  
pp. 2355-2374 ◽  
Author(s):  
C. Weldon Mathews
Keyword(s):  
Absorption Spectrum ◽  
Electronic State ◽  
Ground State ◽  
Band System ◽  
Electronic States ◽  
Vibrational Structure ◽  
Rotational Structure ◽  
Transition Moment ◽  
High Dispersion ◽  
Parallel Type

The absorption spectrum of CF2 in the 2 500 Å region has been photographed at high dispersion, and the rotational structure of a number of bands has been analyzed. The analysis of the well-resolved subbands establishes that these are perpendicular- rather than parallel-type bands, as previously assigned. Further analysis shows that the upper and lower electronic states are of 1B1 and 1A1symmetries respectively, corresponding to a transition moment that is perpendicular to the plane of the molecule. In the upper electronic state, r0(CF) = 1.32 Å and [Formula: see text], while in the ground state, r0(CF) = 1.300 Å and [Formula: see text]. An investigation of the vibrational structure of the band system has shown that the vibrational numbering in ν2′ must be increased by one unit from earlier assignments, thus placing the 000–000 band near 2 687 Å (37 220 cm−1). A search between 1 300 and 8 500 Å showed two new band systems near 1 350 and 1 500 Å which have been assigned tentatively to the CF2 molecule.

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