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Full-Text Articles in Physical Sciences and Mathematics
Competition Between Intra And Intermolecular Triel Bonds. Complexes Between Naphthalene Derivatives And Neutral Or Anionic Lewis Bases, Wiktor Zierkiewicz, Mariusz Michalczyk, Steve Scheiner
Competition Between Intra And Intermolecular Triel Bonds. Complexes Between Naphthalene Derivatives And Neutral Or Anionic Lewis Bases, Wiktor Zierkiewicz, Mariusz Michalczyk, Steve Scheiner
Chemistry and Biochemistry Faculty Publications
A TrF2 group (Tr = B, Al, Ga, In, Tl) is placed on one of the α positions of naphthalene, and its ability to engage in a triel bond (TrB) with a weak (NCH) and strong (NC−) nucleophile is assessed by ab initio calculations. As a competitor, an NH2 group is placed on the neighboring Cα, from which point it forms an intramolecular TrB with the TrF2 group. The latter internal TrB reduces the intensity of the π-hole on the Tr atom, decreasing its ability to engage in a second external TrB. The …
Influence Of Monomer Deformation On The Competition Between Two Types Of Σ-Holes In Tetrel Bonds, Rafal Wysokiński, Mariusz Michalczyk, Wiktor Zierkiewicz, Steve Scheiner
Influence Of Monomer Deformation On The Competition Between Two Types Of Σ-Holes In Tetrel Bonds, Rafal Wysokiński, Mariusz Michalczyk, Wiktor Zierkiewicz, Steve Scheiner
Chemistry and Biochemistry Faculty Publications
One of several tetrel (T) atoms was covalently attached to three F atoms and a substituted phenyl ring. A NH3 base can form a tetrel bond with TF3C6H2R3(T = Si, Ge, Sn, Pb; R = H, F, CH3) in a position opposite either an F atom or the ring. The σ-hole opposite the highly electron-withdrawing F (T-F) is more intense than that opposite the ring (T-C). However, when the Lewis base deforms from a tetrahedral to a trigonal bipyramidal shape so as to accommodate the base, it is the T-C σ-hole that is more intense. Accordingly, it is the T-C …
Dual Geometry Schemes In Tetrel Bonds: Complexes Between Tf4(T = Si, Ge, Sn) And Pyridine Derivatives, Wiktor Zierkiewicz, Mariusz Michalczyk, Rafał Wysokiński, Steve Scheiner
Dual Geometry Schemes In Tetrel Bonds: Complexes Between Tf4(T = Si, Ge, Sn) And Pyridine Derivatives, Wiktor Zierkiewicz, Mariusz Michalczyk, Rafał Wysokiński, Steve Scheiner
Chemistry and Biochemistry Faculty Publications
When an N-base approaches the tetrel atom of TF4(T = Si, Ge, Sn) the latter moleculedeforms from a tetrahedral structure in the monomer to a trigonal bipyramid. The base can situateitself at either an axial or equatorial position, leading to two different equilibrium geometries.The interaction energies are considerably larger for the equatorial structures, up around 50 kcal/mol,which also have a shorter R(T··N) separation. On the other hand, the energy needed to deform thetetrahedral monomer into the equatorial structure is much higher than the equivalent deformationenergy in the axial dimer. When these two opposite trends are combined, it is the axial …
Triel-Bonded Complexes Between Trr3 (Tr = B, Al, Ga; R = H, F, Cl, Br, Ch3) And Pyrazine, Mariusz Michalczyk, Wiktor Zierkiewicz, Steve Scheiner
Triel-Bonded Complexes Between Trr3 (Tr = B, Al, Ga; R = H, F, Cl, Br, Ch3) And Pyrazine, Mariusz Michalczyk, Wiktor Zierkiewicz, Steve Scheiner
Chemistry and Biochemistry Faculty Publications
Complexes between TrR3 (Tr = B, Al, Ga; R= H, F, Cl, Br, CH3)molecules and pyrazine have been characterized at the MP2 and CCSD(T) levels of theory. The adducts can be grouped according to the type of molecular arrangement. The first situation places the Tr atom in the plane of the pyrazine ring and contains a triel bond to the N lone pair. For the boron complexes the orbital interaction energy is almost equal to the electrostatic component, while the former is only half the latter for Tr= Al and Ga. The two monomers are stacked above one another in …
Regium Bonds Between Mn Clusters (M=Cu,Ag,Au And N=2-6) And Nucleophiles Nh3 And Hcn, Wiktor Zierkiewicz, Mariusz Michalczyk, Steve Scheiner
Regium Bonds Between Mn Clusters (M=Cu,Ag,Au And N=2-6) And Nucleophiles Nh3 And Hcn, Wiktor Zierkiewicz, Mariusz Michalczyk, Steve Scheiner
Chemistry and Biochemistry Faculty Publications
The most stable geometries of the coinagemetal (or regium) atom (Cu, Ag, Au) clusters Mn for n up to 6 are all planar, and adopt the lowest possible spin multiplicity. Clusters with even numbers of M atoms are thus singlets, while those with odd n are open-shell doublets. Examination of the molecular electrostatic potential (MEP) of each cluster provides strong indications of the most likely site of attack by an approaching nucleophile, generally one of two positions. A nucleophile (NH3 or HCN) most favorably approaches one particular M atom of each cluster, rather than a bond midpoint or face. In …
Comparison Between Tetrel Bonded Complexes Stabilized By Σ And Π Hole Interactions, Wiktor Zierkiewicz, Mariusz Michalczyk, Steve Scheiner
Comparison Between Tetrel Bonded Complexes Stabilized By Σ And Π Hole Interactions, Wiktor Zierkiewicz, Mariusz Michalczyk, Steve Scheiner
Chemistry and Biochemistry Faculty Publications
The σ-hole tetrel bonds formed by a tetravalent molecule are compared with those involving a π-hole above the tetrel atom in a trivalent bonding situation. The former are modeled by TH4, TH3F, and TH2F2 (T = Si, Ge, Sn) and the latter by TH2=CH2, THF=CH2, and TF2=CH2, all paired with NH3 as Lewis base. The latter π-bonded complexes are considerably more strongly bound, despite the near equivalence of the σ and π-hole intensities. The larger binding energies of the π-dimers are attributed to greater electrostatic attraction and orbital interaction. Each progressive replacement of H by F increases the strength of …
Aerogen Bonds Formed Between Aeof2 (Ae = Kr, Xe) And Diaziness: Comparisons Between Σ-Hole And Π-Hole Complexes, Wiktor Zierkiewicz, Mariusz Michalczyk, Steve Scheiner
Aerogen Bonds Formed Between Aeof2 (Ae = Kr, Xe) And Diaziness: Comparisons Between Σ-Hole And Π-Hole Complexes, Wiktor Zierkiewicz, Mariusz Michalczyk, Steve Scheiner
Chemistry and Biochemistry Faculty Publications
The interaction between KrOF2 or XeOF2 and the 1,2, 1,3, and 1,4 diazines is characterized chiefly by a Kr/Xe···N aerogen bond, as deduced from ab initio calculations. The most stable dimers take advantage of the σ-hole on the aerogen atom, wherein the two molecules lie in the same plane. The interaction is quite strong, as much as 18 kcal mol-1. A second class of dimer geometry utilizes the π-hole above the aerogen atom in an approximate perpendicular arrangement of the two monomers; these structures are not as strongly bound: 6-8 kcal mol-1. Both sorts of dimers contain auxiliary CH···F H-bonds …
Regioselectivity Of The Interaction Of Temozolomide With Borane And Boron Trifluoride, Okuma Emile Kasende, Jules Tshishimbi Muya, Steve Scheiner
Regioselectivity Of The Interaction Of Temozolomide With Borane And Boron Trifluoride, Okuma Emile Kasende, Jules Tshishimbi Muya, Steve Scheiner
Chemistry and Biochemistry Faculty Publications
MP2 and B3LYP calculations are used to predict the most favorable site of temozolomide toward BH3 and BF3 which are classical Lewis acids. Binding energies, charge transfers, and bond length perturbations of the temozolomide in various complexes indicate that the N12 atom is the preferred attack site for BH3, while BF3 prefers the O17 atom. The interactions are quite strong, as much as 100 kJ/mol for BH3 and more than 60 kJ/mol for BF3. The molecular electrostatic potential surrounding temozolomide is most negative around the O atoms, which is unable to explain the energetic order of binding of the Lewis …
Extrapolation To The Complete Basis Set Limit For Binding Energies Of Noncovalent Interactions, Steve Scheiner
Extrapolation To The Complete Basis Set Limit For Binding Energies Of Noncovalent Interactions, Steve Scheiner
Chemistry and Biochemistry Faculty Publications
A means of extrapolating from double and triple-valence basis sets to a complete basis set is examined in the context of the pnicogen bonds in the BH2P⋯NH3 complexes, with B = CH3, H, NH2, CF3, OH, Cl, F, and NO2. Binding energies converge smoothly, and the trends for the various substituents B are unaffected by the basis set size, extrapolation, or level of inclusion of electron correlation, including MP2 and CCSD(T). The approach appears to be successful also for H-bonded systems, in particular the water dimer. In the event that full extrapolation within the context of CCSD(T) is not feasible, …
Primary And Secondary Basis Set Superposition Error At The Scf And Mp2 Levels. H3n‐‐Li+ And H2o‐‐Li+, Zdzisław Latajka, Steve Scheiner
Primary And Secondary Basis Set Superposition Error At The Scf And Mp2 Levels. H3n‐‐Li+ And H2o‐‐Li+, Zdzisław Latajka, Steve Scheiner
Steve Scheiner
The primary basis set superposition error (BSSE) results from the artificial lowering of the energy of each subunit of a pair by the presence of ‘‘ghost orbitals’’ of its partner. In addition, these ghost orbitals perturb the one‐electron properties of the molecule, causing a change in the interaction energy, an effect known as secondary BSSE which is not corrected by the counterpoise procedure. The primary and secondary BSSE are calculated for the interactions of NH3 and H2O with Li+, using a variety of different basis sets. It is found that the 2° BSSE can be …
Primary And Secondary Basis Set Superposition Error At The Scf And Mp2 Levels. H3n‐‐Li+ And H2o‐‐Li+, Z. Latajka, Steve Scheiner
Primary And Secondary Basis Set Superposition Error At The Scf And Mp2 Levels. H3n‐‐Li+ And H2o‐‐Li+, Z. Latajka, Steve Scheiner
Chemistry and Biochemistry Faculty Publications
The primary basis set superposition error (BSSE) results from the artificial lowering of the energy of each subunit of a pair by the presence of ‘‘ghost orbitals’’ of its partner. In addition, these ghost orbitals perturb the one‐electron properties of the molecule, causing a change in the interaction energy, an effect known as secondary BSSE which is not corrected by the counterpoise procedure. The primary and secondary BSSE are calculated for the interactions of NH3 and H2O with Li+, using a variety of different basis sets. It is found that the 2° BSSE can be …
Correction Of The Basis Set Superposition Error In Scf And Mp2 Interaction Energies. The Water Dimer, M. M. Szczesniak, Steve Scheiner
Correction Of The Basis Set Superposition Error In Scf And Mp2 Interaction Energies. The Water Dimer, M. M. Szczesniak, Steve Scheiner
Chemistry and Biochemistry Faculty Publications
There has been some discussion concerning whether basis set superposition error is more correctly evaluated using the full set of ghost orbitals of the partner molecule or some subset thereof. A formal treatment is presented, arguing that the full set is required at the Møller–Plesset level. Numerical support for this position is provided by calculation of the interaction energy between a pair of water molecules, using a series of moderate sized basis sets ranging from 6‐31G∗∗ to the [432/21] contraction suggested by Clementi and Habitz. These energies, at both the SCF and MP2 levels, behave erratically with respect to changes …