Determination of rate constants for photosolvation reactions: solvent dependence of chloride substitution rates for excited states of cis-dichlorobis(2,2'-bipyridine)iridium(III)

1980 ◽  
Vol 102 (24) ◽  
pp. 7264-7268 ◽  
Author(s):  
B. Divisia ◽  
P. C. Ford ◽  
R. J. Watts
Keyword(s):  
Excited States ◽  
Rate Constants ◽  
Substitution Rates ◽  
Solvent Dependence

scholarly journals Theoretical Determination of Rate Constants from Excited-States: Application to Benzophenone

2021 ◽  
Author(s):  
Katsuyuki Shizu ◽  
Hironori Kaji
Keyword(s):  
Excited States ◽  
Rate Constants ◽  
Density Functional ◽  
Golden Rule ◽  
Density Functional Theory Calculations ◽  
Cost Effective ◽  
Functional Theory ◽  
Constant Determination ◽  
Cost Effective Method

A cost-effective method of theoretically predicting electronic transition rate constants from the excited-states of molecules is reported. This method is based on density functional theory calculations of electronic states and quantitative rate constant determination with the Fermi golden rule.

scholarly journals Theoretical Determination of Rate Constants from Excited-States: Application to Benzophenone

2021 ◽  
Author(s):  
Katsuyuki Shizu ◽  
Hironori Kaji
Keyword(s):  
Excited States ◽  
Rate Constants ◽  
Density Functional ◽  
Golden Rule ◽  
Density Functional Theory Calculations ◽  
Cost Effective ◽  
Functional Theory ◽  
Constant Determination ◽  
Cost Effective Method

A cost-effective method of theoretically predicting electronic transition rate constants from the excited-states of molecules is reported. This method is based on density functional theory calculations of electronic states and quantitative rate constant determination with the Fermi golden rule.

Solvent Dependence of Structural Dynamics and Spin-flip Processes in 3,4,5-tri(9H-carbazole-9-yl)benzonitrile (ortho-3CzBN)

2020 ◽  
Author(s):  
Masaki Saigo ◽  
Kiyoshi Miyata ◽  
Hajime Nakanotani ◽  
Chihaya Adachi ◽  
Ken Onda
Keyword(s):  
Dft Calculations ◽  
Excited States ◽  
Structural Changes ◽  
Photophysical Properties ◽  
Delayed Fluorescence ◽  
Time Resolved ◽  
Thermally Activated Delayed Fluorescence ◽  
Thermally Activated ◽  
Solvent Dependence ◽  
Acetonitrile Solutions

We have investigated the solvent-dependence of structural changes along with intersystem crossing of a thermally activated delayed fluorescence (TADF) molecule, 3,4,5-tri(9H-carbazole-9-yl)benzonitrile (o-3CzBN), in toluene, tetrahydrofuran, and acetonitrile solutions using time-resolved infrared (TR-IR) spectroscopy and DFT calculations. We found that the geometries of the S1 and T1 states are very similar in all solvents though the photophysical properties mostly depend on the solvent. In addition, the time-dependent DFT calculations based on these geometries suggested that the thermally activated delayed fluorescence process of o-3CzBN is governed more by the higher-lying excited states than by the structural changes in the excited states.<br>

Determination of rate constants of redox reactions of second order from current-less potential-time curves by a simplified graphical-numerical method

1983 ◽  
Vol 48 (5) ◽  
pp. 1358-1367 ◽  
Author(s):  
Antonín Tockstein ◽  
František Skopal
Keyword(s):  
Numerical Method ◽  
Explicit Form ◽  
Rate Constant ◽  
Optimization Algorithm ◽  
Rate Constants ◽  
Redox Reactions ◽  
Second Order ◽  
Wide Region ◽  
Recurrent Formula

A method for constructing curves is proposed that are linear in a wide region and from whose slopes it is possible to determine the rate constant, if a parameter, θ, is calculated numerically from a rapidly converging recurrent formula or from its explicit form. The values of rate constants and parameter θ thus simply found are compared with those found by an optimization algorithm on a computer; the deviations do not exceed ±10%.

Determination of the Accurate Values of the Rate Constant and Thermodynamic Parameters for the Rotation About the C(sp2)-C(aryl) Bond; Adamantan-1-yl 3-Bromo-2,4,6-trimethylphenyl Ketone

1998 ◽  
Vol 63 (7) ◽  
pp. 955-966
Author(s):  
Eva Přibylová ◽  
Miroslav Holík
Keyword(s):  
Thermodynamic Parameters ◽  
Shape Analysis ◽  
Rate Constants ◽  
Line Shape ◽  
Microsoft Excel ◽  
Hindered Rotation ◽  
H Nmr ◽  
Line Shape Analysis ◽  
Coalescence Temperature

Four programs for the 1H NMR line shape analysis: two commercial - Winkubo (Bruker) and DNMR5 (QCPE 165) and two written in our laboratory - Newton (in Microsoft Excel) and Simtex (in Matlab) have been tested in order to get highly accurate rate constants of the hindered rotation about a single bond. For this purpose four testing criteria were used, two of them were also developed by us. As supplementary determinations the rate constants obtained for the coalescence temperature and for the thermal racemization of chromatographically separated enantiomers were used which fitted well the temperature dependence of the rate constants determined by the line shape analysis. As a test compound adamantan-1-yl 3-bromo-2,4,6-trimethylphenyl ketone was prepared and studied. It was shown that supermodified simplex method used in our algorithm (Simtex), though time consuming, gives the most accurate values of the rate constants and consequently the calculated thermodynamic parameters Ea, ∆H≠, and ∆S≠ lay in relatively narrow confidence intervals.

Determination of the Nucleophilicity of Tricarbonyliron Coordinated Cyclohepta-1,3,5-triene

1999 ◽  
Vol 64 (11) ◽  
pp. 1770-1779 ◽  
Author(s):  
Herbert Mayr ◽  
Karl-Heinz Müller
Keyword(s):  
Gibbs Energy ◽  
Ambient Temperature ◽  
Rate Constants ◽  
Second Order ◽  
Order Rate ◽  
Electrophilic Additions ◽  
Kinetics Of

The kinetics of the electrophilic additions of four diarylcarbenium ions (4a-4d) to tricarbonyl(η4-cyclohepta-1,3,5-triene)iron (1) have been studied photometrically. The second-order rate constants match the linear Gibbs energy relationship log k20 °C = s(E + N) and yield the nucleophilicity parameter N(1) = 3.69. It is concluded that electrophiles with E ≥ -9 will react with complex 1 at ambient temperature.

Interfacial catalysis by phospholipase A2: determination of the interfacial kinetic rate constants

Biochemistry ◽  
1991 ◽  
Vol 30 (29) ◽  
pp. 7283-7297 ◽  
Author(s):  
Otto G. Berg ◽  
Bao Zhu Yu ◽  
Joe Rogers ◽  
Mahendra Kumar Jain
Keyword(s):  
Phospholipase A2 ◽  
Rate Constants ◽  
Kinetic Rate ◽  
Kinetic Rate Constants ◽  
Interfacial Catalysis
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