Computational Study of the Photochemical Fragmentation of Hydantoin

The mechanism of the photochemical fragmentation reaction is investigated theoretically using the model system, hydantoin, using the CAS(22,16)/6-31G(d) and MP2-CAS-(22,16)/6-311G(d)//CAS(22,16)/6-31G(d) methods. The model investigation demonstrates that the preferred reaction route for the photofragmentation reaction is as follows: hydantoin → Franck-Condon region → conical intersection → fragment photoproducts (i.e., CO, isocyanic acid, and methylenimine). The theoretical finding additionally suggests that no organic radicals exist during the fragmentation reaction. Moreover, due to the high activation energy, the theoretical evidences suggest that it would be difficult to yield the three fragments under the thermal reaction. All the above theoretical observations are consistent with the available experimental results

How Important is Metal-Carbon Back-Bonding for the Stability of Fullerene-Transition Metal Complexes? Role of Cage Sizes, Encapsulated Ions and Metal Ligands

A density functional study of {η2-(X@Cn)}ML2 complexes with various cage sizes (C60, C70, C76, C84, C90, C96), encapsulated ions (X = F−, 0, Li+) and metal fragments (M = Pt, Pd) is performed, using M06/LANL2DZ levels of theory. The importance of π back-bonding to the thermodynamic stability of fullerene-transition metal complexes ({η2-(X@Cn)}ML2) and the effect of encapsulated ions, metal fragments and cage sizes on the π back-bonding are determined in this study. The theoretical computations suggest that π back-bonding plays an essential role in the formation of fullerene-transition metal complexes. The theoretical evidence also suggests that there is no linear correlation between cage sizes and π back-bonding, but the encapsulated Li+ ion enhances π back-bonding and F− ion results in its deterioration. These computations also show that a platinum center produces stronger π back-bonding than a palladium center. It is hoped that the conclusions that are provided by this study can be used in the design, synthesis and growth of novel fullerene-transition complexes

The Effect of Substituent on Molecules That Contain a Triple Bond Between Arsenic and Group 13 Elements: Theoretical Designs and Characterizations

The effect of substitution on the potential energy surfaces of RE13≡AsR (E13 = group 13 elements; R = F, OH, H, CH3, and SiH3) is determined using density functional theory (M06‐2X/Def2‐TZVP, B3PW91/Def2‐TZVP, and B3LYP/LANL2DZ+dp). The computational studies demonstrate that all triply bonded RE13≡AsR species prefer to adopt a bent geometry that is consistent with the valence electron model. The theoretical studies also demonstrate that RE13≡AsR molecules with smaller substituents are kinetically unstable, with respect to the intramolecular rearrangements. However, triply bonded R′E13≡AsR′ species with bulkier substituents (R′ = SiMe(SitBu3)2, SiiPrDis2, and NHC) are found to occupy the lowest minimum on the singlet potential energy surface, and they are both kinetically and thermodynamically stable. That is to say, the electronic and steric effects of bulky substituents play an important role in making molecules that feature an E13≡As triple bond as viable synthetic target

The Triply Bonded Al☰Sb Molecules: A Theoretical Prediction

The effect of substitution on the potential energy surfaces of RAl☰SbR (R = F, OH, H, CH3, SiH3, SiMe(SitBu3)2, SiiPrDis2, Tbt, and Ar*) is investigated using density functional theories (M06-2X/Def2-TZVP, B3PW91/Def2-TZVP, and B3LYP/LANL2DZ + dp). The theoretical results demonstrated that all the triply bonded RAl☰SbR compounds with small substituents are unstable and can spontaneously rearrange to other doubly bonded isomers. That is, the smaller groups, such as R = F, OH, H, CH3 and SiH3, neither kinetically nor thermodynamically stabilize the triply bonded RAl☰SbR compounds. However, the triply bonded R’Al☰SbR´ molecules that feature bulkier substituents (R´ = SiMe(SitBu3)2, SiiPrDis2, Tbt, and Ar*) are found to possess the global minimum on the singlet potential energy surface and are both kinetically and thermodynamically stable. In particular, the bonding characters of the R’Al☰SbR´ species agree well with the valence-electron bonding model (model) as well as several theoretical analyses (the natural bond orbital, the natural resonance theory, and the charge decomposition analysis). That is to say, R’Al☰SbR´ molecules that feature groups are regarded as R′─Al Sb─R′. Their theoretical evidence shows that both the electronic and the steric effects of bulkier substituent groups play a decisive role in making triply bonded R′Al☰SbR′ species synthetically accessible and isolable in a stable form

Simulations Suggest Possible Triply Bonded Phosphorus≡E13 Molecules (E13 = B, Al, Ga, In, and Tl)

The effect of substitution on the potential energy surfaces of RE13 ☰ PR (E13 = B, Al, Ga, In, Tl; R = F, OH, H, CH3, SiH3, SiMe(SitBu3)2, SiiPrDis2, Tbt, and Ar* is studied using density functional theory (M06-2X/Def2-TZVP, B3PW91/Def2-TZVP and B3LYP/LANL2DZ + dp). The theoretical results demonstrate that all triply bonded RE13 ☰ PR compounds with small substituents are unstable and spontaneously rearrange to other doubly bonded isomers. That is, the smaller groups, such as R 〓 F, OH, H, CH3 and SiH3, neither kinetically nor thermodynamically stabilize the triply bonded RE13 ☰ PR compounds. However, the triply bonded R’E13☰PR´ molecules, possessing bulkier substituents (R´ = SiMe(SitBu3)2, SiiPrDis2, Tbt and Ar*), are found to have a global minimum on the singlet potential energy surface. In particular, the bonding character of the R’E13☰PR´ species is well defined by the valence-electron bonding model (model [II]). That is to say, R’E13☰PR´ molecules that feature groups are regarded as R′-E13P-R′. The theoretical evidence shows that both the electronic and the steric effects of bulkier substituent groups play a prominent role in rendering triply bonded R′E13☰PR′ species synthetically accessible and isolable in a stable form

The Mechanisms for the Oxidative Addition of Imidazolium Salts to a Group 9 Transition Metal Atom (Co0, Rh0, and Ir0) and a Group 10 Transition Metal Atom (Ni0, Pd0, and Pt0): A Theoretical Study

The potential energy surfaces of the oxidative addition reactions, L2M + imidazoliumcation → product and CpM′L + imidazolium cation → product (M = Ni, Pd, Pt; M′ = Co, Rh, Ir; Cp = η5-C5H5; L = 1,3-aryl-N-heterocyclic carbene (NHC), aryl = 2,4,6-trimethylphenyl), are studied at the M06-L/Def2-SVP level of theory. The theoretical findings show that the singlet-triplet splitting (∆Est = Etriplet − Esinglet) for the L2M and CpM′L species can be used to predict the reactivity for their oxidative additions. That is to say, current theoretical evidence suggests that both a 14-electron L2M complex and a 16-electron CpM′Lcomplex with a better electron-donating ligand L (such as NHC) result in a reduced ∆Est value and facilitate the oxidative addition to the saturated C─H bond. The theoretical results for this study are in good agreement with the obtainable experimental results and allow a number of predictions to be made

Theoretical Investigations of Mechanisms for the Reactions of Seven-Member Ring N-Heterocyclic Carbene and Its Heavier Analogues

The potential energy surfaces for the chemical reactions of group 14 carbenes were studied using density functional theory (B3LYP/LANL2DZ + dp). Five group 14 carbene species containing a seven-member ring, 7-Rea-E, where E = C, Si, Ge, Sn and Pb, were chosen as model reactants for this work. Three types of chemical reactions (water addition, imine cycloaddition and dimerization) were used to study the reactivity of these 7-Rea-E molecules. Present theoretical investigations suggest that the relative reactivity of carbenes decreases in the order: 7-Rea-C > 7-Rea-Si > 7-Rea-Ge > 7-Rea-Sn > 7-Rea-Pb. That is, the heavier the group 14 atom (E), the more stable its corresponding 7-Rea-E compound to chemical reaction. This study’s theoretical findings suggest that all of the seven-member 7-Rea-E should be readily synthesized and isolated at room temperature, since they are quite inert to chemical reaction, except for reaction with moisture. Furthermore, the group 14 7-Rea-E singlet-triplet energy splitting, as described in the configuration-mixing model of Pross and Shaik, can be used as a diagnostic tool to predict their reactivity. The results obtained allow a number of predictions to be made

Triple Bonds between Bismuth and Group 13 Elements: Theoretical Designs and Characterization

The effect of substitution on the potential energy surfaces of RE13≡BiR (E13 = B, Al, Ga, In, and Tl; R = F, OH, H, CH3, SiH3, Tbt, Ar*, SiMe(SitBu3)2, and SiiPrDis2) is investigated using density functional theories (M06-2X/Def2-TZVP, B3PW91/Def2-TZVP, and B3LYP/LANL2DZ+dp). The theoretical results suggest that all of the triply bonded RE13≡BiR molecules prefer to adopt a bent geometry (i.e., ∠RE13Bi ≈ 180° and ∠E13BiR ≈ 90°), which agrees well with the bonding model (model (B)). It is also demonstrated that the smaller groups, such as R = F, OH, H, CH3, and SiH3, neither kinetically nor thermodynamically stabilize the triply bonded RE13≡BiR compounds, except for the case of H3SiB≡BiSiH3. Nevertheless, the triply bonded RʹE13≡BiRʹ molecules that feature bulkier substituents (Rʹ = Tbt, Ar*, SiMe(SitBu3)2, and SiiPrDis2) are found to have the global minimum on the singlet potential energy surface and are both kinetically and thermodynamically stable. In other words, both the electronic and the steric effects of bulkier substituent groups play an important role in making triply bonded RE13≡BiR (Group 13–Group 15) species synthetically accessible and isolable in a stable form

An Efficient Fitness Function in Genetic Algorithm Classifier for Landuse Recognition on Satellite Images

Genetic algorithm (GA) is designed to search the optimal solution via weeding out the worse gene strings based on a fitness function. GA had demonstrated effectiveness in solving the problems of unsupervised image classification, one of the optimization problems in a large domain. Many indices or hybrid algorithms as a fitness function in a GA classifier are built to improve the classification accuracy. This paper proposes a new index, DBFCMI, by integrating two common indices, DBI and FCMI, in a GA classifier to improve the accuracy and robustness of classification. For the purpose of testing and verifying DBFCMI, well-known indices such as DBI, FCMI, and PASI are employed as well for comparison. A SPOT-5 satellite image in a partial watershed of Shihmen reservoir is adopted as the examined material for landuse classification. As a result, DBFCMI acquires higher overall accuracy and robustness than the rest indices in unsupervised classification