Structures and stability of N9, N9 − and N9 + clusters

 Ab initio molecular orbital calculations for N₉, N⁻ ₉ and N⁺ ₉ isomers were carried out at the HF/ 6-31G*, B3PW91/6-31G*, B3LYP/6-31G* and MP2/ 6-31G* levels of theory. Stable equilibrium geometric structures were determined by harmonic vibrational frequency analyses at the HF/6-31G*, B3PW91/6-31G* and B3LYP/6-31G* levels of theory. The most stable free-radical N₉ cluster is structure 1 with C _{2 v} symmetry and that of anion N⁻ ₉ is structure 3 with C _s symmetry. Only one stable structure of the N⁺ ₉ cation with C _{2 v} symmetry was predicted. Their potential application as high-energy-density materials has been examined. Received: 15 June 1999 / Accepted: 11 October 1999 / Published online: 14 March 2000     

A molecular orbital rationalization of ligand effects in N2 activation

Molecular orbital theory has been used to study a series of [(micro-N2){ML3}2] complexes as models for dinitrogen activation, with M=Mo, Ta, W, Re and L=NH2, PH2, AsH2, SbH2 and N(BH2)2. The main aims of this study have been to provide a thorough electronic analysis of the complexes and to extend previous work involving molecular orbital analyses. Molecular orbital diagrams have been used to rationalize why for L=NH2 ligand rotation is important for the singlet state but not the triplet, to confirm the effect of ligand pi donation, and to rationalize the importance of the metal d-electron configuration. The outcomes of this study will assist with a more in-depth understanding of the electronic basis for N2 activation and allow clearer predictions to be made about the structure and multiplicity of systems involved in transition-metal catalysis.     

Comment on “Analytical evaluation for two-center nuclear attraction integrals over Slater type orbitals by using Fourier transform method” by S. ?zcan and E. ?ztekin (J. Math. Chem. DOI 10.1007/s10910-008-9398-z)

S. ?zcan and E. ?ztekin, (J. Math. Chem. doi:) published formulas for evaluating the two-center nuclear attraction integrals over Slater type orbitals. It is shown that the analytical relations for these integrals through the expansion coefficients of the electron charge density for the one-center case and the overlap integrals presented in Sect. 3 of this work can easily be derived by means of a simple algebra from the formulas published in our papers (I.I. Guseinov, J Mol Struct (Theochem) 417:117, 1997; J Math Chem 42:415, 2007 and B.A. Mamedov, Chin J Chem 22:545, 2004). It should be noted that the formulas of overlap integrals presented by E. ?ztekin et al., in previous paper (E. ?ztekin, M. Yavuz, Ş. Atalay, J Mol Struct (Theochem) 544:69, 2001) for the calculation of two-center nuclear attraction integrals also are obtained from our papers (see Comment: I.I. Guseinov, J Mol Struct (Theochem) 638:235, 2003).     

Electronegativity Scaled as a Average Attracting Energy of Valence‐Shell Electrons in a Ground‐State Free Atom

The total capability of an atom attracting valence electrons can be measured by the sum of ionization energies of valence electron in a ground‐state free atom plus its electron affinity called Total Attracting Energy, TAE = Σn_iE_i + EA, where, E_i is the ionization energy of the ith valence‐shell electron in a ground‐state free atom, n_i is the number of valence‐shell electron bearing energy E_i, and EA is the electron affinity. And the electronegativity χ_CL is proportional to the average of TAE, AAE = TAE_av, divided by Σn_i, the number of atomic valence‐shell electrons. χ_CL = 0.1813 TAE_av = 0.1813 AAE = 0.1813 TAE/Σn_i, = 0.1813 (Σn_iE_I + EA)/Σn_i. Further, the atomic valence orbital electronegativity can be also obtained from the TAE value of an atom. Some discussions were made on several special aspects such as scale of rare gases, comparisons with Pauling's and Allen's scales, etc.     

A theoretical study of angiotensin-converting enzyme inhibitors

Summary INDO molecular orbital calculations are reported for 35 selected angiotensin-converting enzyme inhibitors. QSARs are developed between pI₅₀ data and molecular electronic indices. The QSARs obtained reflect the importance of both charge-charge interactions between inhibitor and receptor and of specific interactions between groups on the inhibitor with points around the molecule which are postulated to correspond to binding sites at the receptor.     

2-Pyridone and 3-oxo-1,2,6-thiadiazine-1,1-dioxide derivatives: a new class of hydrogen bond equivalents of uracil

Hydrogen bond complex stability between adenine (A) and hydrogen bond equivalents of uracil: 2-pyridone derivatives (U^X _X2O) and 3-oxo-1,2,6-thiadiazine-1,1-dioxide derivatives (U^X _SO2) was studied, and as the result, the hydrogen bond energy of U^X _X2O-A and a complex of UX^X _SO2-A, was about 1.5 kcal/mol more stable than that of the corresponding adenine-uracil derivatives complex, respectively. The energy difference between the imide tautomer and enol tautomer was smaller than those of uracil derivatives. U^F _SO2 can form a stable complex with A, and its imide tautomer is stable.     

Conformational analysis of methylphenidate: comparison of molecular orbital and molecular mechanics methods

Summary Methylphenidate (MP) binds to the cocaine binding site on the dopamine transporter and inhibits reuptake of dopamine, but does not appear to have the same abuse potential as cocaine. This study, part of a comprehensive effort to identify a drug treatment for cocaine abuse, investigates the effect of choice of calculation technique and of solvent model on the conformational potential energy surface (PES) of MP and a rigid methylphenidate (RMP) analogue which exhibits the same dopamine transporter binding affinity as MP. Conformational analysis was carried out by the AM1 and AM1/SM5.4 semiempirical molecular orbital methods, a molecular mechanics method (Tripos force field with the dielectric set equal to that of vacuum or water) and the HF/6-31G* molecular orbital method in vacuum phase. Although all three methods differ somewhat in the local details of the PES, the general trends are the same for neutral and protonated MP. In vacuum phase, protonation has a distinctive effect in decreasing the regions of space available to the local conformational minima. Solvent has little effect on the PES of the neutral molecule and tends to stabilize the protonated species. The random search (RS) conformational analysis technique using the Tripos force field was found to be capable of locating the minima found by the molecular orbital methods using systematic grid search. This suggests that the RS/Tripos force field/vacuum phase protocol is a reasonable choice for locating the local minima of MP. However, the Tripos force field gave significantly larger phenyl ring rotational barriers than the molecular orbital methods for MP and RMP. For both the neutral and protonated cases, all three methods found the phenyl ring rotational barriers for the RMP conformers/invertamers (denoted as cte, tte, and cta) to be: cte, tte> MP > cta. Solvation has negligible effect on the phenyl ring rotational barrier of RMP. The B3LYP/6-31G* density functional method was used to calculate the phenyl ring rotational barrier for neutral MP and gave results very similar to those of the HF/6-31G* method.     

Thermal stabilities,electronic properties and structures of metformin-metal complexes

The atomic superposition and electron delocalization molecular orbital (ASED-MO) theory was used to calculate structures and relative stabilities of metformin-metal complexes. The relative stabilities and decomposition pathways were discussed in terms of bond order, binding energy and the nature of charge on the central metal atom. The electronic transitions and their energy gaps were also studied. The optimization of the structures shows that the most stable state is distorted from planarity for Co^II and Ni^II complexes.     

Reply to “Comment on ‘Calculation of Two-center Nuclear Attraction Integrals over Integer and Noninteger N-slater-type Orbitals in Nonlined-up Coordinate Systems” ’

The comments of Guseinov on our recent paper (T. Özdo?an, S. Gümü? and M. Kara, J. Math. Chem. 33 (2003) 181) are critically analyzed. It is proved that the expansion formula for the product of two normalized associated Legendre functions and the expressions for two-center nuclear attraction integrals over Slater type orbitals have been obtained independently, by the use of basic mathematical rules.