Electron-phonon interactions in photoinduced excited electronic states in fluoroacenes

The electron-phonon coupling constants [l(B1u(HOMO-->LUMO))] in the photoinduced excited electronic states in fluoroacenes are estimated and compared with those in the monoanions (l(LUMO)) and cations (l(HOMO)). The l(B1u(HOMO-->LUMO)) values are much larger than the l(LUMO) and l(HOMO) values in fluoroacenes. Furthermore, the Coulomb pseudopotential mu* values for the excited electronic states are estimated to be smaller than those for the monoanions and cations. The complete phase patterns difference between the highest occupied molecular orbitals (HOMOs) and the lowest unoccupied molecular orbitals (LUMOs) is the main reason why the electron-phonon coupling constants and the mu* values are larger and smaller, respectively, in the photoinduced excited electronic states than in the monoanions and cations. The possible electron pairing and Bose-Einstein condensation in the excited electronic states of fluoroacenes are discussed. Because of larger electron-phonon coupling constants and smaller mu* values in the excited electronic states than in the charged states, the conditions under which the electron-electron interactions become attractive can be more easily realized, in principle, in the excited electronic states than in the charged states in fluoroacenes. The l(B1u(HOMO-->LUMO)) values hardly change by H-F substitution, even though the l(LUMO) and l(HOMO) values significantly increase by H-F substitution in acenes. Antibonding interactions between carbon and fluorine atoms in the HOMO and LUMO are the main reason why the l(B1u(HOMO-->LUMO)) values hardly change by H-F substitution in acenes.     

Transition Structures for the Aromatic Claisen Rearrangements by the Molecular Orbital Method

Ab initio calculations were performed for eight Claisen rearrangements, eqs 1-8. Transition-state (TS) structures of [3,3] sigmatropic rearrangements of reactions 1-4 are similar, but their activation energies (E(a)'s) are different, E(a)(1) < E(a)(2) and E(a)(3) < E(a)(4). From the intermediate of reaction 3, a hydrogen is moved intermolecularly to form the product, o-allyl phenol. The lower reactivities of reactions 2 and 4 relative to reactions 1 and 3 are ascribed to large endothermicities in the sigmatropic rearrangements, respectively. Chair-type transition states are more favorable than boat-type transition states in reactions 1-4. The allyl group is released from the in-plane C-X (X = O or N) sigma bond and is captured by the pi-type lone-pair electrons. The sulfur- and phosphorus-containing rearrangements, reactions 5-8, are computed to have smaller activation energies but are to be less exothermic than those of oxgyen- and nitrogen-containing rearrangements.     

A theoretical study on the photodissociation of C3O2

The photodecomposition of C₃O₂ into C₂O and CO is studied with the ab initio MO calculation. It is found that, starting from the second excited state of C₃O₂ (_u), the ground-state C₂O (triplet) is yielded through the bent dissociation. The stable structure of the excited triplet state of C₃O₂ as an intermediate is also demonstrated.     

First observation of clusters for solvated tropylium ions

We have first observed clusters for solvated tropylium ions (Tr+(ROH)n) which were isolated from ROH-CH3CN (1:1 by vol.; R = Me, Et, and Prn) solutions by using a specially designed mass spectrometer and found the clear-cut essential features concerning the solvation structure around Tr+.     

A note on the theory of interatomic long-range forces

A comment is made on the multipolar expansion formula of the long-range force between hydrogen atoms previously obtained. The second-order perturbation energy neglecting exchange in the framework of the Unsöld approximation is evaluated exactly. An extension is made to helium atoms, and to other s-electron interactions. An approximate method is suggested to estimate the interatomic force between two atoms in general.     

A DFT study of the hydrolysis of hydantoin

Density functional theory (DFT) calculations were made on the hydrolysis of hydantoin (2,4-imidazolidinedione). In the neutral hydrolysis, reacting systems composed of hydantoin and (H₂O)_n with n = 1+3, 2+3, 3+3, and 4+3 were adopted. Three water molecules (“+3”) participate in the in-plane hydrogen-bond circuit, and the n–3 = 1, 2, 3 or 4 water cluster works for the out-of-plane nucleophilic attack onto the carbonyl carbon of hydantoin. Transition states (TSs) involving bond interchanges prompted by proton transfers were determined. The reaction path with n = 3+3 containing N-carbamoyl glycine, N-carboxy glycine and three tetrahedral intermediates was found to be most likely. In the acid-catalyzed hydrolysis, a reacting system composed of hydantoin and H₃O⁺(H₂O)₇ was employed. Ten TSs and nine intermediates were obtained. N-carbamoyl glycine and N-carboxy glycine were confirmed to be detectable stable species. The product consists of glycine, carbonic acid (not CO₂), NH₄⁺, and (H₂O)₅. It has the exothermic energy, whereas the product in the neutral hydrolysis is of the endothermic one for all n values. For both neutral (n = 3+3) and acid-catalyzed hydrolyses, the rate-determining steps were calculated to be for formation of the tetrahedral intermediate, HOOC-CH₂-NH-C(OH)₂NH₂. The pattern of proton transfers along hydrogen bonds was carefully investigated.     

Electron-phonon interactions in the monocations of polyacetylenes

Electron-phonon interactions in the monocations of trans-polyacetylenes such as C2H4 (2tpa), C4H6 (2tpa), C6H8 (6tpa), and C8H10 (8tpa) are studied. The C-C stretching Ag modes around 1700 cm(-1) afford the largest electron-phonon coupling constants in the monocations of polyacetylenes. However, the C-C bending Ag modes around 1200 cm(-1) afford much smaller electron-phonon coupling constants than the C-C stretching Ag modes around 1700 cm(-1) in the monocations of polyacetylenes. The total electron-phonon coupling constants for the monocations (l HOMO) are estimated to be 0.357, 0.285, 0.281, and 0.279 eV for 2tpa, 4tpa, 6tpa, and 8tpa, respectively. The l HOMO values for polyacetylenes with C 2h geometry hardly change with an increase in molecular size while those for polyacenes with D 2h geometry significantly decrease with an increase in molecular size. The l HOMO values for polyacetylenes are larger than those for polyacenes. The calculated results are rationalized in terms of the phase patterns of the molecular orbitals in detail. The electron transfer in the positively charged polyacetylenes is also discussed. Intramolecular electron mobility (sigma(intra,monocation)) in the positively charged polyacetylenes is estimated to be smaller than those for the positively charged polyacenes. The reorganization energies for the positively charged polyacetylenes are estimated to be larger than those for the positively charged polyacenes. Thus, the larger overlap integrals between two neighboring molecules are needed for the positively charged polyacetylenes to become good conductor than those for positively charged polyacenes. On the other hand, the conditions under which the electron-electron interactions are attractive are more easily realized in the monocations of polyacetylenes than in the monocations of polyacenes. The quality as conducting materials would not significantly depend on the molecular size in the positively charged polyacetylenes, compared with that in the positively charged polyacenes. Multimode problem is also treated in order to investigate how consideration of multimode problem is closely related to the characteristics of the electron-phonon interactions.     

Ultrasonic density measurement cell design and simulation of non-ideal effects

This paper presents a theoretical analysis of a density measurement cell using an unidimensional model composed by acoustic and electroacoustic transmission lines in order to simulate non-ideal effects. The model is implemented using matrix operations, and is used to design the cell considering its geometry, materials used in sensor assembly, range of liquid sample properties and signal analysis techniques. The sensor performance in non-ideal conditions is studied, considering the thicknesses of adhesive and metallization layers, and the effect of residue of liquid sample which can impregnate on the sample chamber surfaces. These layers are taken into account in the model, and their effects are compensated to reduce the error on density measurement. The results show the contribution of residue layer thickness to density error and its behavior when two signal analysis methods are used.     

Correlation between the rate order and the number of molecules in the reaction of trimethyl phosphite with water in acetonitrile solvent

Density functional theory calculations of the title reaction, P(OCH?)? + (H?O)(n) in CH?CN, were conducted, where n is the number of water molecules. Two routes, the routes suggested by (A) Aksnes and (B) Arbuzov, were traced with various n values. Both routes consist of two transition states (TSs) and one intermediate. Route B was found to be more likely than route A. In the former, the activation free energy (ΔG(?)) of n = 3 is slightly smaller than that of n = 2. The n = 3 TS geometry is composed of a nucleophile H?O, a proton donor H?O, and an auxiliary one. Indeed, the geometry appears to be plausible for ready proton relays along hydrogen bonds, but it is inconsistent with the observed third-order rate constant. Catalytic water molecules were added to the n = 2 and 3 bond-interchange circuits. Then route B with n = 2 + 2 was found to be best. By n = 2 + 10 and n = 3 + 12 models, the n = 2 based route B was confirmed to be likely.