Toward organic photohydrides: excited-state behavior of 10-methyl-9-phenyl-9,10-dihydroacridine.

The excited-state hydride release from 10-methyl-9-phenyl-9,10-dihydroacridine (PhAcrH) was investigated using steady-state and time-resolved UV/vis absorption spectroscopy. Upon excitation, PhAcrH is oxidized to the corresponding iminium ion (PhAcr(+)), while the solvent (acetonitrile/water mixture) is reduced (52% of PhAcr(+) and 2.5% of hydrogen is formed). The hydride release occurs from the triplet excited state by a stepwise electron/hydrogen-atom transfer mechanism. To facilitate the search for improved organic photohydrides that exhibit a concerted mechanism, a computational methodology is presented that evaluates the thermodynamic parameters for the hydride ion, hydrogen atom, and electron release from organic hydrides.

Electronic states of the benzene dimer: a simple case of complexity.

Electronic structure calculations of the excited states of the benzene dimer using equation-of-motion coupled-cluster method are reported. The calculations reveal large density of electronic states, including multiple valence, Rydberg, and mixed Rydberg-valence states. The calculations of the oscillator strengths for the transitions between the excimer state (i.e., the lowest excited state of the dimer, 1(1)B(1g)) and other excited states allowed us to identify the target state responsible for the excimer absorption as the E(1u) state of a mixed Rydberg-valence character at 3.04 eV above the excimer (1(1)B(1g)). Although at D(6h) the 1(1)B(1g) → E(1u) transition is symmetry-forbidden, small geometric displacements (to D(2h)) that have a negligible effect on the excitation energy split this degenerate state into the dark (4B(3u)) and bright (4B(2u)) components (oscillator strength of 0.3 au). The excitation energy for this transition depends strongly on the dimer structure, which explains the broad character of the experimentally observed excimer absorption spectrum.

Effect of hyperconjugation on ionization energies of hydroxyalkyl radicals.

On the basis of electronic structure calculations and molecular orbital analysis, we offer a physical explanation of the observed large decrease (0.9 eV) in ionization energies (IE) in going from hydroxymethyl to hydroxyethyl radical. The effect is attributed to hyperconjugative interactions between the sigma CH orbitals of the methyl group in hydroxyethyl, the singly occupied p orbital of carbon, and the lone pair p orbital of oxygen. Analyses of vertical and adiabatic IEs and hyperconjugation energies computed by the natural bond orbital (NBO) procedure reveal that the decrease is due to the destabilization of the singly occupied molecular orbital in hydroxyethyl radical as well as structural relaxation of the cation maximizing the hyperconjugative interactions. The stabilization is achieved due to the contraction of the CO and CC bonds, whereas large changes in torsional angles bear little effect on the total hyperconjugation energies and, consequently, IEs.

Exploring the correlation between network structure and electron binding energy in the (H(2)O)(7)(-) cluster through isomer-photoselected vibrational predissociation spectroscopy and ab initio calculations: addressing complexity beyond types I-III.

We report a combined photoelectron and vibrational spectroscopy study of the (H(2)O)(7)(-) cluster anions in order to correlate structural changes with the observed differences in electron binding energies of the various isomers. Photoelectron spectra of the (H(2)O)(7)(-) . Ar(m) clusters are obtained over the range of m=0-10. These spectra reveal the formation of a new isomer (I') for m>5, the electron binding energy of which is about 0.15 eV higher than that of the type I form previously reported to be the highest binding energy species [Coe et al., J. Chem. Phys. 92, 3980 (1990)]. Isomer-selective vibrational predissociation spectra are obtained using both the Ar dependence of the isomer distribution and photochemical depopulation of the more weakly (electron) binding isomers. The likely structures of the isomers at play are identified with the aid of electronic structure calculations, and the electron binding energies, as well as harmonic vibrational spectra, are calculated for 28 low-lying forms for comparison with the experimental results. The HOH bending spectrum of the low binding type II form is dominated by a band that is moderately redshifted relative to the bending origin of the bare water molecule. Calculations trace this feature primarily to the bending vibration localized on a water molecule in which a dangling H atom points toward the electron cloud. Both higher binding forms (I and I') display the characteristic patterns in the bending and OH stretching regions signaling electron attachment primarily to a water molecule in an AA binding site, a persistent motif found in non-isomer-selective spectra of the clusters up to (H(2)O)(50)(-).

On the contribution of vibrational anharmonicity to the binding energies of water clusters.

The second-order vibrational perturbation theory method has been used together with the B3LYP and MP2 electronic structure methods to investigate the effects of anharmonicity on the vibrational zero-point energy (ZPE) contributions to the binding energies of (H2O)n, n = 2-6, clusters. For the low-lying isomers of (H2O)6, the anharmonicity correction to the binding energy is calculated to range from -248 to -355 cm(-1). It is also demonstrated that although high-order electron correlation effects are important for the individual vibrational frequencies, they are relatively unimportant for the net ZPE contributions to the binding energies of water clusters.

Dipole-bound anions of highly polar molecules: ethylene carbonate and vinylene carbonate.

Results of experimental and theoretical studies of dipole-bound negative ions of the highly polar molecules ethylene carbonate (EC, C3H4O3, mu=5.35 D) and vinylene carbonate (VC, C3H2O3, mu=4.55 D) are presented. These negative ions are prepared in Rydberg electron transfer (RET) reactions in which rubidium (Rb) atoms, excited to ns or nd Rydberg states, collide with EC or VC molecules to produce EC- or VC- ions. In both cases ions are produced only when the Rb atoms are excited to states described by a relatively narrow range of effective principal quantum numbers, n*; the greatest yields of EC- and VC- are obtained for n*(max)=9.0+/-0.5 and 11.6+/-0.5, respectively. Charge transfer from low-lying Rydberg states of Rb is characteristic of a large excess electron binding energy (Eb) of the neutral parent; employing the previously derived empirical relationship Eb=23/n*(max)(2.8) eV, the electron binding energies are estimated to be 49+/-8 meV for EC and 24+/-3 meV for VC. Electron photodetachment studies of EC- show that the excess electron is bound by 49+/-5 meV, in excellent agreement with the RET results, lending credibility to the empirical relationship between Eb and n*(max). Vertical electron affinities for EC and VC are computed employing aug-cc-pVDZ atom-centered basis sets supplemented with a (5s5p) set of diffuse Gaussian primitives to support the dipole-bound electron; at the CCSD(T) level of theory the computed electron affinities are 40.9 and 20.1 meV for EC and VC, respectively.