scholarly journals Picosecond Laser Study of Thioindigoid Dyes Photoisomerization

1984 ◽  
Vol 4 (1-6) ◽  
pp. 121-128 ◽  
Author(s):  
S. A. Krysanov ◽  
M. V. Alfimov
Keyword(s):  
Quantum Yield ◽  
Rate Constant ◽  
Time Domain ◽  
Singlet State ◽  
Picosecond Laser ◽  
Intersystem Crossing ◽  
Transient Species ◽  
Triplet Mechanism ◽  
The Time Domain ◽  
Cis Isomer

The transient species in the trans ⇌ cis photoisomerization of the perinaphto–thioindigoid dye were identified by picosecond laser spectroscopy in the time domain 10 ps–5 ns. An excitation of the trans isomer with a 6 ps, 528 nm pulse to the singlet state S1 (the peak of S′n ← S1 absorption at 700 nm) results in the intersystem crossing S1 ⇝ T1 (the peak of Tn ← T1 absorption at 730 nm) with the quantum yield of 0.7 and rate constant (1.4 ± 0.3)· 109s−1. An excitation of the cis isomer results also in the intersystem crossing (the peak of Tn> ← T1 absorption at 670 nm) with the rate constant (3.7 ± 1.2)· 1010s−1. The triplet mechanism of the photoisomerization in the both directions is proposed.

Photolysis of ketene. I

1968 ◽  
Vol 46 (14) ◽  
pp. 2353-2360 ◽  
Author(s):  
A. N. Strachan ◽  
D. E. Thornton
Keyword(s):  
Carbon Monoxide ◽  
Quantum Yield ◽  
Triplet State ◽  
Singlet State ◽  
Inert Gases ◽  
Inert Gas ◽  
Excited Singlet State ◽  
Intersystem Crossing ◽  
Excited Singlet ◽  
Increasing Temperature

Ketene has been photolyzed at 3660 and 3130 Å both alone and in the presence of the inert gases C4F8 and SF6. The quantum yield of carbon monoxide has been determined at both wavelengths as a function of pressure and temperature. At 3660 Å the quantum yield decreases with increasing pressure but increases with increasing temperature. At 3130 Å the quantum yield with ketene alone remains 2.0 at both 37 and 100 °C at pressures up to 250 mm. At higher pressures of ketene or with added inert gas the quantum yield decreases with increasing pressure. The results are interpreted in terms of a mechanism in which intersystem crossing from the excited singlet state to the triplet state occurs at both wavelengths, and collisional deactivation of the excited singlet state by ketene is single stage at 3660 Å but multistage at 3130 Å.

Fluorescence of chloropentafluoroacetone

1970 ◽  
Vol 48 (16) ◽  
pp. 2611-2616 ◽  
Author(s):  
H. S. Samant ◽  
A. J. Yarwood
Keyword(s):  
Rate Constant ◽  
High Pressures ◽  
Singlet State ◽  
Radiative Lifetime ◽  
Heavy Atom ◽  
Excited Singlet State ◽  
Intersystem Crossing ◽  
Excited Singlet ◽  
Gaseous State ◽  
Fluorescent State

The fluorescence of chloropentafluoroacetone in the gaseous state at room temperature is reported. The fluorescence extends from 337 nm to greater than 560 nm with a maximum intensity at 420 nm and is unaffected by low pressures of oxygen. The energy of the first excited singlet state is estimated as about 83 kcal and the fluorescence data for 313 and "290" nm excitation indicate that fluorescence enhancement occurs as the pressure increases. The fluorescent yield at high pressures [Formula: see text] is independent of the nature of the gas used to attain the high pressure. The lifetime of the fluorescent state is 35.1 ± 0.3 ns.A simple mechanism correlates the experimental observations and the values of the rate constants are considered. The reciprocal of the natural radiative lifetime is calculated to be 6.6 × 105 s−1 and the rate constant assigned to intersystem crossing to the triplet is 2.8 × 107 s−1. A comparison with the data in the literature for hexafluoroacetone shows the effect of substitution by a heavy atom in the fluorinated ketone. It about doubles the value of the rate constant associated with intersystem crossing from the first excited singlet state in the gas phase.

The primary process in the photolysis of hexafluoroacetone vapour III. The efficiency of intersystem crossing

1968 ◽  
Vol 306 (1487) ◽  
pp. 529-536 ◽  
Keyword(s):  
Quantum Yield ◽  
Lower Limit ◽  
Singlet State ◽  
Excited Singlet State ◽  
Intersystem Crossing ◽  
Primary Process ◽  
Excited Singlet ◽  
A Value ◽  
Low Concentrations

The value of k 6 /( k 4 + k 5 + k 6 ) (mechanism of part I) was determined by two techniques, namely the sensitization of the isomerization of cis - to trans -butene-2 and the sensitization of the phosphorescence of biacetyl. Both techniques yielded a value for the ratio of 0⋅9 ± 0⋅1. The value obtained by the isomerization technique is a lower limit because the quantum yield for the isomerization did not attain a value independent of [ cis -butene-2], but reached a maximum at low concentrations of olefine and then decreased. A similar scavenging of the excited singlet state of hexafluoroacetone was observed when biacetyl was present as an addend. However, in both cases the measurements were made with sufficiently low concentrations of addend that the singlet scavenging should have introduced less, than 10% error. It is concluded that reaction (5) of the mechanism cannot be an important mode of disappearance of excited ketone molecules.

Photocyanation of 3,4-dimethoxy-1-nitrobenzene. A quantitative study

1986 ◽  
Vol 51 (2) ◽  
pp. 358-367 ◽  
Author(s):  
Petr Kuzmič ◽  
Milan Souček
Keyword(s):  
Quantum Yield ◽  
Quantitative Study ◽  
Rate Constant ◽  
Potassium Cyanide ◽  
Intersystem Crossing ◽  
Excited Triplet ◽  
Cyanide Anion ◽  
Tert Butanol ◽  
Diffusion Controlled ◽  
Triplet Lifetime

UV photolysis (365 nm) of 3,4-dimethoxy-1-nitrobenzene in the presence of potassium cyanide leading to 3-cyano-4-methoxy-1-nitrobenzene was subjected to a quantitative photokinetic study. The reaction exhibits a second order kinetics with respect to the nucleophile and is effectively quenched by molecular oxygen as well as 2,4-hexadienoic acid. The excited triplet lifetime of 0.9 microseconds was determined on the basis of the dependence of quantum yield on the nucleophile and quencher concentrations in 50% aqueous tert-butanol. The quantum yield of intersystem crossing is at least 0.38 in the same solvent; bimolecular rate constant for the interaction of triplet 3,4-dimethoxy-1-nitrobenzene with cyanide anion has the value of 5.6 . 108 l . mol-1s-1, which is approximately one half of the rate constant for diffusion controlled quenching. Quantum yield of the reaction is strongly dependent on the water content in mixtures with tert-butanol and increases from 0.04 in water to 0.68 in 88% tert-butanol.

Apodisation in the time domain

1992 ◽  
Vol 2 (4) ◽  
pp. 615-620
Author(s):  
G. W. Series
Keyword(s):  
Time Domain ◽  
The Time Domain

JOINT INTERPRETATION OF AIRBORNE ELECTROMAGNETIC DATA IN THE TIME DOMAIN AND FREQUENCY DOMAIN

2018 ◽  
Vol 12 (7-8) ◽  
pp. 76-83
Author(s):  
E. V. KARSHAKOV ◽  
J. MOILANEN
Keyword(s):  
Fourier Transform ◽  
Frequency Domain ◽  
Time Domain ◽  
Frequency Interval ◽  
Single Spectrum ◽  
Simultaneous Inversion ◽  
Homogeneous Half Space ◽  
Time Domain Data ◽  
The Time Domain

Тhe advantage of combine processing of frequency domain and time domain data provided by the EQUATOR system is discussed. The heliborne complex has a towed transmitter, and, raised above it on the same cable a towed receiver. The excitation signal contains both pulsed and harmonic components. In fact, there are two independent transmitters operate in the system: one of them is a normal pulsed domain transmitter, with a half-sinusoidal pulse and a small "cut" on the falling edge, and the other one is a classical frequency domain transmitter at several specially selected frequencies. The received signal is first processed to a direct Fourier transform with high Q-factor detection at all significant frequencies. After that, in the spectral region, operations of converting the spectra of two sounding signals to a single spectrum of an ideal transmitter are performed. Than we do an inverse Fourier transform and return to the time domain. The detection of spectral components is done at a frequency band of several Hz, the receiver has the ability to perfectly suppress all sorts of extra-band noise. The detection bandwidth is several dozen times less the frequency interval between the harmonics, it turns out thatto achieve the same measurement quality of ground response without using out-of-band suppression you need several dozen times higher moment of airborne transmitting system. The data obtained from the model of a homogeneous half-space, a two-layered model, and a model of a horizontally layered medium is considered. A time-domain data makes it easier to detect a conductor in a relative insulator at greater depths. The data in the frequency domain gives more detailed information about subsurface. These conclusions are illustrated by the example of processing the survey data of the Republic of Rwanda in 2017. The simultaneous inversion of data in frequency domain and time domain can significantly improve the quality of interpretation.

scholarly journals Broadband spectroscopy of astrophysical ice analogues

2019 ◽  
Vol 629 ◽  
pp. A112 ◽  
Author(s):  
B. M. Giuliano ◽  
A. A. Gavdush ◽  
B. Müller ◽  
K. I. Zaytsev ◽  
T. Grassi ◽  
...  
Keyword(s):  
Refractive Index ◽  
Optical Properties ◽  
Time Domain ◽  
Complex Refractive Index ◽  
Far Infrared ◽  
Infrared Region ◽  
Thz Radiation ◽  
The Real ◽  
Thz Range ◽  
The Time Domain

Context. Reliable, directly measured optical properties of astrophysical ice analogues in the infrared and terahertz (THz) range are missing from the literature. These parameters are of great importance to model the dust continuum radiative transfer in dense and cold regions, where thick ice mantles are present, and are necessary for the interpretation of future observations planned in the far-infrared region. Aims. Coherent THz radiation allows for direct measurement of the complex dielectric function (refractive index) of astrophysically relevant ice species in the THz range. Methods. We recorded the time-domain waveforms and the frequency-domain spectra of reference samples of CO ice, deposited at a temperature of 28.5 K and annealed to 33 K at different thicknesses. We developed a new algorithm to reconstruct the real and imaginary parts of the refractive index from the time-domain THz data. Results. The complex refractive index in the wavelength range 1 mm–150 μm (0.3–2.0 THz) was determined for the studied ice samples, and this index was compared with available data found in the literature. Conclusions. The developed algorithm of reconstructing the real and imaginary parts of the refractive index from the time-domain THz data enables us, for the first time, to determine the optical properties of astrophysical ice analogues without using the Kramers–Kronig relations. The obtained data provide a benchmark to interpret the observational data from current ground-based facilities as well as future space telescope missions, and we used these data to estimate the opacities of the dust grains in presence of CO ice mantles.

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