scholarly journals Theoretical study on mechanism of the photochemical ligand substitution of fac-[ReI(bpy)(CO)3(PR3)]+ complex

2016 ◽  
Vol 18 (26) ◽  
pp. 17557-17564 ◽  
Author(s):  
Kenichiro Saita ◽  
Yu Harabuchi ◽  
Tetsuya Taketsugu ◽  
Osamu Ishitani ◽  
Satoshi Maeda
Keyword(s):  
Theoretical Study ◽  
Dft Method ◽  
Ligand Substitution ◽  
Ligand Dissociation ◽  
Td Dft ◽  
Dominant Process

The mechanism of the CO ligand dissociation of fac-[ReI(bpy)(CO)3P(OMe)3]+ has theoretically been investigated, as the dominant process of the photochemical ligand substitution (PLS) reactions of fac-[ReI(bpy)(CO)3PR3]+, by using the (TD-)DFT method.

Hybridization and de-hybridization between the locally-excited (LE) state and the charge-transfer (CT) state: a combined experimental and theoretical study

2016 ◽  
Vol 18 (35) ◽  
pp. 24176-24184 ◽  
Author(s):  
Yu Gao ◽  
Shitong Zhang ◽  
Yuyu Pan ◽  
Liang Yao ◽  
Haichao Liu ◽  
...  
Keyword(s):  
Charge Transfer ◽  
Theoretical Study ◽  
Dft Method ◽  
Locally Excited ◽  
Gradual Evolution ◽  
Td Dft

Gradual evolution of hybridization process between the LE and CT states is investigated in a series of TPA–PI (HxVy) derivatives by TD-DFT method.

Quantum-Chemical Ab Initio Calculations on Inda- and Thallabenzene (C5H5In and C5H5Tl) and their Structural Isomers η5-C5H5In and η5-C5H5Tl

2018 ◽  
Vol 71 (3) ◽  
pp. 102
Author(s):  
Emma Persoon ◽  
Yuekui Wang ◽  
Gerhard Raabe
Keyword(s):  
Ab Initio ◽  
Quantum Chemical ◽  
Density Functional ◽  
Single Point ◽  
Normal Modes ◽  
Dft Method ◽  
Basis Sets ◽  
Triplet States ◽  
Structural Isomers ◽  
Td Dft

Quantum-chemical ab initio, time-independent, as well as time-dependent density functional theory (TD-DFT) calculations were performed on the so far elusive heterocycles inda- and thallabenzene (C5H5In and C5H5Tl), employing several different methods (MP2, CISD, CCSD, CCSD(T), BD, BD(T), QCISD, QCISD(T), CASSCF, DFT/B3LYP), effective core potentials, and different basis sets. While calculations on the MP2 level predict the ground states of the title compounds to be singlets with the first triplet states between 13 and 15 kcal mol−1 higher in energy, single point calculations with the QCISD(T), CCSD(T), and BD(T) methods at CCSD-optimized structures result in energy differences between the singlet and the triplet states in the range between 0.3 and 2.1 kcal mol−1 in favour of the triplet states. According to a CASSCF(8,8) calculation the triplets are also more stable by about 2.5–2.9 kcal mol−1. Calculations were also performed for the C5v-symmetric η5 structural isomers (cyclopentadienylindium, CpIn, and cyclopentadienylthallium, CpTl, Cp = C5H5) of the title compounds. At the highest level of theory employed in this study, C5H5In is between 79 and 88 kcal mol−1 higher in energy than CpIn, while this energy difference is even larger for thallabenzene where C5H5Tl is energetically between 94 and 102 kcal mol−1 above CpTl. In addition we report on the UV/vis spectra calculated with a TD-DFT method as well as on the spectra of the normal modes of C5H5In and C5H5Tl. Both types of spectra might facilitate identification of the title compounds eventually formed in photolysis or pyrolysis experiments.

scholarly journals Theoretical Study of the Reaction of Formation of Some Free Phosphines by Stereoselective Hydrophosphination through DFT Method

2018 ◽  
pp. 1-10
Author(s):  
Kouadio Valery Bohoussou ◽  
Anoubilé Bénié ◽  
Mamadou Guy-Richard Koné ◽  
N’guessan Yao Silvère Diki ◽  
Kafoumba Bamba ◽  
...  
Keyword(s):  
Theoretical Study ◽  
Chemical Reactivity ◽  
Dft Method ◽  
Trans Form ◽  
Dft Methods ◽  
Activation Barriers ◽  
Reactivity Descriptors ◽  
Chemical Reactivity Descriptors ◽  
Theoretical Results ◽  
Cis Isomer

In this work the formation of vinylphosphines was studied through the hydrophosphination reaction. The study aims to rationalize the stereoselectivity of these compounds using quantum DFT methods. This theoretical study of chemical reactivity was conducted at B3LYP/6-311 + G (d, p) level. Global chemical reactivity descriptors, stationary point energies and activation barriers were examined to foretell the relative stability of the stereoisomers formed. The various results obtained have revealed that the addition of arylphosphine to dihalogenoacetylene is stereospecific. The Trans form of vinylphosphines is more stable than the Cis form, when the substituent on phosphorus generates less or no π-conjugations. On the other hand, the Cis isomer is predominant when the aryl radical favors more π-conjugations. The theoretical results obtained are in agreement with the experimental results.

Investigating the photolysis of NO2 and influencing factors by using a DFT/TD-DFT method

2020 ◽  
Vol 230 ◽  
pp. 117559
Author(s):  
Xiaoxiang Wang ◽  
Lei Zhou ◽  
Yifan Liu ◽  
Kun Zhang ◽  
Guangli Xiu
Keyword(s):  
Influencing Factors ◽  
Dft Method ◽  
Td Dft

scholarly journals Surface-enhanced Raman scattering of pyrazine on Au5Al5 bimetallic nanoclusters

RSC Advances ◽  
2017 ◽  
Vol 7 (20) ◽  
pp. 12170-12178 ◽  
Author(s):  
Quanjiang Li ◽  
Qianqian Ding ◽  
Weihua Lin ◽  
Jiangcai Wang ◽  
Maodu Chen ◽  
...  
Keyword(s):  
Density Functional ◽  
Dft Method ◽  
Time Dependent ◽  
Functional Theory ◽  
Bimetallic Nanoclusters ◽  
Surface Enhanced ◽  
Td Dft ◽  
Surface Enhanced Raman ◽  
Enhanced Raman Scattering ◽  
Dependent Density

In this study, we theoretically investigated the Raman and absorption spectra of pyrazine adsorbed on Au5Al5 bimetallic nanoclusters by a time-dependent density functional theory (TD-DFT) method.

An analogy study on ESIPT reaction for 3BHC sensor between polar DMF and nonpolar toluene

2017 ◽  
Vol 95 (12) ◽  
pp. 1303-1307
Author(s):  
Dapeng Yang ◽  
Min Jia ◽  
Jingyuan Wu ◽  
Xiaoyan Song ◽  
Qiaoli Zhang
Keyword(s):  
Excited State ◽  
Density Functional ◽  
Emission Spectra ◽  
Dft Method ◽  
Intramolecular Proton Transfer ◽  
Nonpolar Solvent ◽  
State Behavior ◽  
Functional Theory ◽  
Td Dft ◽  
Intramolecular Hydrogen

A comparison about excited state intramolecular proton transfer (ESIPT) mechanism of a new sensor 3-(1,3-benzothiazol-2-yl)-2-hydroxynaphthalene-1-carbaldehyde (3BHC) in polar solvent dimethylformamide (DMF) and nonpolar solvent toluene have been investigated within the framework of the time-dependent density functional theory (TD-DFT) method. The reproduced previous experimental absorption and emission spectra via our calculations reveals the reasonability of the DFT and TD-DFT theoretical level. The staple bond lengths, bond angles, and corresponding infrared vibrational spectra demonstrate that the intramolecular hydrogen bond of 3BHC should be strengthened in both polar DMF and nonpolar toluene. Two kinds of ESIPT mechanisms for different solvents have been put forward; there is a low potential barrier in the ESIPT process in the DMF solvent, whereas there is almost a nonbarrier for the ESIPT process in the toluene solvent. Hence, we could conclude that the ESIPT process of 3BHC sensor is more likely to occur in the nonpolar solvent upon the photoexcitation, based on which, the excited state behavior of 3BHC could be controlled.

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