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H F Schaefer

Publications and source records attributed to H F Schaefer.

10 recordsLinked to original sources
PubMed2006

Monobridged Si2H4.

The rotational spectrum of a new monobridged isomer of Si(2)H(4), denoted here as H(2)Si(H)SiH, has been detected by Fourier transform microwave spectroscopy of a supersonic molecular beam through the discharge products of silane. On the basis of high-level coupled cluster theory, this isomer is calculated to lie only 7 kcalmol above disilene (H(2)SiSiH(2)), the most stable isomeric arrangement of Si(2)H(4), and to be fairly polar, with a calculated dipole moment of mu = 1.14 D. The rotational spectrum of H(2)Si(H)SiH exhibits closely spaced line doubling, characteristic of a molecule undergoing high-frequency inversion. Transition state calculations indicate that inversion probably occurs in two steps: migration of the bridged hydrogen atom to form silylsilylene, H(3)SiSiH, and then internal rotation of the SiH(3) group, followed by the reverse process. The potential energy surface for this type of inversion is quite shallow, with a barrier height of only 2-3 kcalmol. Searches for the rotational lines of silylsilylene, calculated to be of comparable stability to H(2)Si(H)SiH but about five times less polar (mu = 0.23 D), have also been undertaken, so far without success, even though strong lines of H(2)Si(H)SiH have been detected. The favorable energetics and high polarity of monobridged Si(2)H(4) with respect to either disilene or silylsilylene make it a plausible candidate for radioastronomical detection in sources such as IRC + 10216, where comparably large silicon molecules such as SiS, SiC(3), and SiC(4) have already been discovered.

Journal Article↗
PubMed2001

Analysis of the origin of through-space proton NMR deshielding by selected organic functional groups.

GIAO-HF and IGLO-DFT computations of isotropic magnetic shieldings were used to map the NMR shielding environments of small molecules exemplifying selected organic functional groups. Two different probes were employed: a methane molecule and NICS (nucleus-independent chemical shifts) based on computed absolute isotropic shieldings. The reason for the different results obtained using these two probes is perturbation of the wave function by the proximity of methane to the pi bond, as analyzed by the localized orbital contributions to the shieldings. [structure: see text]

Journal Article↗
PubMed2001

Binuclear homoleptic copper carbonyls Cu(2)(CO)(x) (x = 1-6): remarkable structures contrasting metal-metal multiple bonding with low-dimensional copper bonding manifolds.

Binuclear homoleptic copper carbonyls Cu(2)(CO)(x) (x = 1-6) have been studied using four different density functional theory methods (DFT) in conjunction with a basis set of extended double-zeta plus polarization quality, labeled as DZP. For each homoleptic binuclear copper carbonyl compound, several stationary point structures are presented, and these structures are characterized in terms of their geometries, thermochemistry, and vibrational frequencies. The optimal unsaturated Cu(2)(CO)(x) (x = 1-6) structures are generated by joining 18-electron tetrahedral, 16-electron trigonal, 14-electron linear copper carbonyl building blocks, and/or bare copper atoms with copper-copper single bonds rather than by joining 18-electron copper carbonyl units with multiple copper-copper bonds. For Cu(2)(CO)(6) the eclipsed and staggered ethane-like structure are virtually degenerate and lie significantly lower in energy than other possible structures. The eclipsed Cu-Cu single bond distance is predicted to be 2.61 A, while that for the staggered structure is 2.65 A. The lowest energy structure for Cu(2)(CO)(5) is the eclipsed ethyl radical-like structure, with r(e)(Cu-Cu) = 2.51 A. The staggered ethyl radical-like structure lies only 0.1 kcal/mol higher in energy, with a Cu-Cu distance shorter by only approximately 0.001 A. For Cu(2)(CO)(4) a methylcarbene-like structure is predicted to lie lowest, with Cu-Cu distance 2.40 A. However, twisted and planar ethylene-like structure lie only 3-5 kcal/mol higher. For Cu(2)(CO)(3) a surprising methylcarbyne-like structure with r(e)(Cu-Cu) = 2.38 A is predicted to lie lowest with all four DFT methods. However, a classical vinyl radical-like lies only 2-4 kcal/mol higher. For Cu(2)(CO)(2) theory predicts a vinylidene-like structure with r(e)(Cu-Cu) = 2.34 A to be essentially degenerate with cis and trans bent acetylene structures with copper-copper distances 2.33 A. Finally, and consistent with earlier theoretical studies, the linear end on Cu-Cu-CO structure with r(e)(Cu-Cu) = 2.27 A is the predicted global minimum for Cu(2)(CO).

Journal Article↗
PubMed2001

The almost bottleable triplet carbene: 2,6-dibromo-4-tert-butyl-2',6'-bis(trifluoromethyl)-4'-isopropyldiphenylcarbene.

Computations on 2,6-dibromo-4-tert-butyl-2',6'-bis(trifluoromethyl)-4'-isopropyldiphenylcarbene (1) using ab initio and density functional theory methods underscore the unusual stability of the triplet over the singlet state. At the B3LYP/6-311G(d,p) level, the triplet state had a slightly bent central C-C-C bond angle of 167 degrees, whereas this angle in the singlet was 134 degrees. The B3LYP singlet-triplet splitting (12.2 kcal/mol) was larger than that of the parent molecule (5.8 kcal/mol), diphenylcarbene (2), which also has a triplet ground state. The energy of a suitable isodesmic reaction showed the triplet and singlet states of (1) to be destabilized, by 6.3 and 12.5 kcal/mol, respectively, due to the combined effects of the CF3, Br, and alkyl substituents. The linear-coplanar form of (3)(1), which might facilitate dimerization or electrophilic attack at the more exposed diradical center, was prohibitively (35.9 kcal/mol) higher in energy. Our results confirm Tomioka's conclusion that the triplet diarylcarbene, ortho-substituted with bulky CF3 and Br substituents, is persistent due to steric protection of the diradical center. Dimerization and other possible reaction pathways are inhibited, not only by the bulky ortho substituents but also by the para alkyl groups. The increase in stability of the triplet ((3)(1)) state relative to the singlet ((1)(1)) state does not influence the reactivity directly.

Journal Article↗
PubMed2001

Electron affinities of the DNA and RNA bases.

Adiabatic electron affinities (AEAs) for the DNA and RNA bases are predicted by using a range of density functionals with a double-zeta plus polarization plus diffuse (DZP++) basis set in an effort to bracket the true EAs. Although the AEAs exhibit moderate fluctuations with respect to the choice of functional, systematic trends show that the covalent uracil (U) and thymine (T) anions are bound by 0.05-0.25 eV while the adenine (A) anion is clearly unbound. The computed AEAs for cytosine (C) and guanine (G) oscillate between small positive and negative values for the three most reliable functional combinations (BP86, B3LYP, and BLYP), and it remains unclear if either covalent anion is bound. AEAs with B3LYP/TZ2P++ single points are 0.19 (U), 0.16 (T), 0.07 (G), -0.02 (C), and -0.17 eV (A). Favorable comparisons are made to experimental estimates extrapolated from photoelectron spectra data for the complexes of the nucleobases with water. However, experimental values scaled from liquid-phase reduction potentials are shown to overestimate the AEAs by as much as 1.5 eV. Because the uracil and thymine covalent EAs are in energy ranges near those of their dipole-bound counterparts, preparation and precise experimental measurement of the thermodynamically stable covalent anions may prove challenging.

Base Pairing↗
PubMed2001

The photohydration of N-alkylpyridinium salts: theory and experiment.

Bicyclic aziridines formed by the irradiation of pyridinium salts in basic solution have recently been recognized to have great synthetic potential. We have undertaken a joint computational and experimental investigation of the mechanism of this photoreaction. We have computationally determined the structures and relative energies of the relevant stationary points on the lowest potential energy surface (PES) of the pyridinium and methylpyridinium ions. Two important intermediates are shown to be bound minima on the ground-state PES: azoniabenzvalene and a 6-aza[3.1.0]bicyclic ion with an exo-oriented substituent (analogous to prefulvene). We advance a mechanism which involves initial formation of this exo-bicyclic ion, followed by nitrogen migration around the ring via the azoniabenzvalene intermediate. Thus, the barrier separating the two intermediates is the factor that determines the degree of scrambling observed in the photoproducts when the carbon atoms are labeled with deuterium or substituted with additional methyl groups. For N-methylpyridinium, the exo-methyl bicyclic ion was computed to be approximately 1 kcalmol(-1) lower in energy than N-methyl-azoniabenzvalene. The transition state was computed to lie several kcal mol(-1) above the exo-methyl bicyclic ion (+8.4kcalmol(-1), 6-31G* RHF; +3.7kcalmol(-1), 6-31G* B3LYP), but still well below the energy available from the 254 nm excitation of the N-methylpyridinium ion. The computed relative energies correspond splendidly with several experimental findings which include the preference for exo products, the results of deuterium labeling, and the impact of additional substituent methyl groups on the product distribution.

Journal Article↗
PubMed2001

A combined crossed molecular beam and ab initio investigation of C2 and C3 elementary reactions with unsaturated hydrocarbons--pathways to hydrogen deficient hydrocarbon radicals in combustion flames.

Crossed molecular beam experiments on dicarbon and tricarbon reactions with unsaturated hydrocarbons acetylene, methylacetylene, and ethylene were performed to investigate the dynamics of channels leading to hydrogen-deficient hydrocarbon radicals. In the light of the results of new ab initio calculations, the experimental data suggest that these reactions are governed by an initial addition of C2/C3 to the pi molecular orbitals forming highly unsaturated cyclic structures. These intermediates are connected via various transition states and are suggested to ring open to chain isomers which decompose predominantly by displacement of atomic hydrogen, forming C4H, C5H, HCCCCCH2, HCCCCCCH3, H2CCCCH and H2CCCCCH. The C2(1 sigma g+) + C2H4 reaction has no entrance barrier and the channel leading to the H2CCCCH product is strongly exothermic. This is in strong contrast with the C3(1 sigma g+) + C2H4 reaction as this is characterized by a 26.4 kJ mol-1 threshold to form a HCCCCCH2 isomer. Analogous to the behavior with ethylene, preliminary results on the reactions of C2 and C3 with C2H2 and CH3CCH showed the H-displacement channels of these systems to share many similarities such as the absence/presence of an entrance barrier and the reaction mechanism. The explicit identification of the C2/C3 vs. hydrogen displacement demonstrates that hydrogen-deficient hydrocarbon radicals can be formed easily in environments like those of combustion processes. Our work is a first step towards a systematic database of the intermediates and the reaction products which are involved in this important class of reactions. These findings should be included in future models of PAH and soot formation in combustion flames.

Journal Article↗
PubMed1975

Theoretical studies of metal-phosphate interactions: interaction of Li+, Na+, K+, Be++, Mg++, and Ca++ with H2PO4- and (CH3O)2PO2-: implications for nucleic acid solvation.

Model phosphate-metal solvation complexes have been studied by ab-initio self-consistent-field techniques. The complexes studied include (RO)2PO2-(R = H or CH3) with Li+, Na+, K+, Be++, Mg++, Ca++, H2O, and Cl-. The geometries of the complexes were chosen to approximate reasonable model solvation complexes for phosphate groups in a nucleic acid environment. Calculated energies of formation vary as Be++ greater than Mg++ greater than Ca++ greater than Li+ greater than Na+ greater than K+ for all isostructural complexes, consistent with experimental binding trends. These results suggest that site binding of this type can successfully account for the relative specificities of ion binding in polynucleotides and other phosphate-containing molecules.

Beryllium↗
PubMed1974

Barrier Height for the Exchange Reaction F + HF --> FH + F.

There exists a body of conflicting data as to the existence or nonexistence of FHF, ClHCl, BrHBr, and IHI as chemically bound molecular species. Ab initio quantum mechanical electronic structure calculations are presented which predict linear symmetric FHF to be unstable. The barrier height for the F + HF exchange reaction is suggested to be no less than 18 kcal/mol, much larger than expected either intuitively or on the basis of certain experiments on related systems. The expected reliability of the calculations is based upon comparable results for diatomic molecules and the F + H(2) and H + F(2) potential energy surfaces.

Journal Article↗