Open Access. Powered by Scholars. Published by Universities.®
Physical Sciences and Mathematics Commons™
Open Access. Powered by Scholars. Published by Universities.®
Articles 1 - 5 of 5
Full-Text Articles in Physical Sciences and Mathematics
Pi Tetrel Bonds, And Their Influence On Hydrogen Bonds And Proton Transfers, Yuanxin Wei, Qingzhong Li, Steve Scheiner
Pi Tetrel Bonds, And Their Influence On Hydrogen Bonds And Proton Transfers, Yuanxin Wei, Qingzhong Li, Steve Scheiner
Chemistry and Biochemistry Faculty Publications
The positive region that lies above the plane of F2TO (T=C and Si) interacts with malondialdehyde (MDA), which contains an intramolecular H‐bond. The T atom of F2TO can lie either in the MDA molecular plane, forming a T⋅⋅⋅O tetrel bond, or F2TO can stack directly above MDA in a parallel arrangement. The former structure is more stable than the latter, and in either case, F2SiO engages in a much stronger interaction than does F2CO, reaching nearly 200 kJ mol−1. The π‐tetrel bond strengthens/weakens the MDA H‐bond when the bond is formed to the hydroxyl/carbonyl group of MDA, and causes an …
Tetrel, Chalcogen, And Ch⋅⋅O Hydrogen Bonds In Complexes Pairing Carbonyl-Containing Molecules With 1, 2, And 3 Molecules Of Co2, L. M. Azofra, Steve Scheiner
Tetrel, Chalcogen, And Ch⋅⋅O Hydrogen Bonds In Complexes Pairing Carbonyl-Containing Molecules With 1, 2, And 3 Molecules Of Co2, L. M. Azofra, Steve Scheiner
Chemistry and Biochemistry Faculty Publications
The complexes formed by H2CO, CH3CHO, and (CH3)2CO with 1, 2, and 3 molecules of CO2 are studied by ab initio calculations. Three different types of heterodimers are observed, most containing a tetrel bond to the C atom of CO2, and some supplemented by a CH⋅⋅O H-bond. One type of heterodimer is stabilized by an anti-parallel arrangement of the C=O bonds of the two molecules. The binding energies are enhanced by methyl substitution on the carbonyl, and vary between 2.4 and 3.5 kcal/mol. Natural bond orbital analysis identifies a prime source of interaction as charge transfer into the π*(CO) antibonding …
Contributions Of Various Noncovalent Bonds To The Interaction Between An Amide And S-Containing Molecules, U. Adhikari, Steve Scheiner
Contributions Of Various Noncovalent Bonds To The Interaction Between An Amide And S-Containing Molecules, U. Adhikari, Steve Scheiner
Chemistry and Biochemistry Faculty Publications
N-Methylacetamide, a model of the peptide unit in proteins, is allowed to interact with CH3SH, CH3SCH3, and CH3SSCH3 as models of S-containing amino acid residues. All of the minima are located on the ab initio potential energy surface of each heterodimer. Analysis of the forces holding each complex together identifies a variety of different attractive forces, including SH⋅⋅⋅O, NH⋅⋅⋅S, CH⋅⋅⋅O, CH⋅⋅⋅S, SH⋅⋅⋅π, and CH⋅⋅⋅π H-bonds. Other contributing noncovalent bonds involve charge transfer into σ* and π* antibonds. Whereas some of the H-bonds are strong enough that they represent the sole attractive force in several dimers, albeit not usually in the …
Comparison Of Methods For Calculating The Properties Of Intramolecular Hydrogen Bonds. Excited State Proton Transfer, T. Kar, Steve Scheiner, M. Cuma
Comparison Of Methods For Calculating The Properties Of Intramolecular Hydrogen Bonds. Excited State Proton Transfer, T. Kar, Steve Scheiner, M. Cuma
Chemistry and Biochemistry Faculty Publications
A series of molecules related to malonaldehyde, containing an intramolecular H-bond, are used as the testbed for a variety of levels of ab initio calculation. Of particular interest are the excitation energies of the first set of valence excited states, nπ∗ and ππ∗, both singlet and triplet, as well as the energetics of proton transfer in each state. Taking coupled cluster results as a point of reference, configuration interaction-singles–second-order Møller–Plesset (CIS–MP2) excitation energies are too large, as are CIS to a lesser extent, although these approaches successfully reproduce the order of the various states. The …
Ab Initio Comparison Of H Bonds And Li Bonds. Complexes Of Lif, Licl, Hf, And Hcl With Nh3, Z. Latajka, Steve Scheiner
Ab Initio Comparison Of H Bonds And Li Bonds. Complexes Of Lif, Licl, Hf, And Hcl With Nh3, Z. Latajka, Steve Scheiner
Chemistry and Biochemistry Faculty Publications
Ab initio calculations are carried out on the complexes H3N–LiF, H3N–LiCl and their analogs H3N–HF and H3N–HCl as well as the isolated subunits. Double‐zeta basis sets, augmented by two sets of polarization functions, are used in conjunction with second‐order Moller–Plesset perturbation theory (MP2) for evaluation of electron correlation effects. The Li bonds are found to be substantially stronger than their H‐bonding counterparts, due in large measure to the greater dipole moments of the LiX subunits. Correlation has a large effect on the geometry and energetics of …