We present a new methodology, called “direct ab initio dynamics, ” for calculations of thermal rate constants and related properties from first principles. The new method is based on full variational transition state theory plus multidimensional semiclassical tunneling transmission coefficients with the potential energy information to be calculated from an accurate level of ab initio electronic...

The potential energy surface (PES) for the phenyl + propyne reaction, which might contribute to the growth of polycyclic aromatic hydrocarbons (PAHs) under a wide variety of reaction conditions, is described. The PES was characterized at the B3LYP-DFT/6-31G(d) and B3LYP-DFT/6-311+G(d,p) levels of theory. The energies of the entrance transition states, a direct hydrogen-transfer channel and two ...

The results of a systematic study of molecular properties by density functional theory (DFT) are presented and discussed. Equilibrium geometries, dipole moments, harmonic vibrational frequencies, and atomization energies were calculated for a set of 32 small neutral molecules by six different local and gradient-corrected DFT methods, and also by the ab initio methods Hartree-Fock, second-order ...

Ab initio calculations using 6-311G**, cc-pVDZ, and aug-cc-pVDZ, with (MP2, QCISD, CCSD(T)) and without (UHF) electron correlation, and density functional methods (BHandHLYP and B3LYP) predict that cyclization of the 5-aza-5-hexenoyl and (E)-6-aza-5-hexenoyl radicals proceed to afford the 5-exo products. At the CCSD(T)/cc-pVDZ//BHandHLYP/cc-pVDZ level of theory, energy barriers (deltaE(double d...

The HO(3) and HO(4) polyoxide radicals have attracted some attention due to their potential role in ozone chemistry. Experimentally, the geometrical structure of HO(3) is known whereas that of HO(4) is not. Moreover, the existence of the latter radical has been questioned. Theoretical calculations on the two species have been reported before, showing important structural differences depending o...

The constrained density functional theory–configuration interaction (CDFT-CI) method has previously been used to calculate ground-state energies and barrier heights, and to describe electronic excited states, in particular conical intersections. However, the method has been limited to evaluating the electronic energy at just a single nuclear configuration, with the gradient of the energy being ...

The most-studied organocopper, methylcopper (CH(3)Cu), has been synthesized for the first time as a monomer, free of other ligands or coordinated solvent, and detected using millimeter-wave rotational spectroscopy. The molecule was created in the gas phase by the reaction of copper vapor and several different precursors, including CH(4) and tetramethylsilane. An obvious symmetric top pattern wa...

Accurate and precise ionization energies of methylamines (CH3NH2 and CH3ND2) are determined to be 9.042260.0012 and 9.053260.0012 eV, respectively, by ~1118! two-photon mass-analyzed threshold ionization ~MATI! spectroscopy. From selective ionizations from specified intermediate quantum states, fundamental frequencies of amino-wagging and CH3-rocking modes of CH3NH2 1 (CH3ND2 ) in D0 states are...

The force matching method is used to improve density functional theory (DFT) by designing a supplemental potential to capture the difference in atomic forces between a DFT functional and a high-quality post Hartree-Fock method. The supplemental potential has two-body terms designed to correct for dispersion and hydrogen bond interactions. The potential also has one-body terms to improve the des...

The results are reported of an ab initio study of the addition of LiAlH(4) to acetonitrile and malononitrile at the MP2(full)/6-311+G* level considering the effects of electron correlation at higher levels up to QCISD(T)/6-311++G(2df,2pd) and including ether solvation. All imide (RCH(2)CH═N(-)) and enamide (RCH(-)CH═NH ↔ RCH═CHN(-)H) adducts feature strong interactions between the organic anion...