Description: This article discusses collaborations. Over the past 40 years, much of the author's research, both computational and experimental, has involved collaborations. This Perspective describes some of the author's collaborative research in eight different areas of organic and theoretical chemistry: (1) hydrocarbons containing unsaturatively, 1,3-bridged cyclobutane rings, (2) the use of orbital topology for predicting the ground states of diradicals, (3) violations of Hund's rule, (4) the chemistry of phenylnitrenes, (5) tunneling by carbon in organic reactions, (6) the Cope rearrangement and the effect of substituents on it, (7) pyramidalized alkenes, dehydrocubanes, cubyl cation, and octanitrocubane, and (8) the effects of geminal fluorine substitution at C-2 of 1,3-diradicals. Highlighted in this Perspective are the synergism between calculations and experiments in the author's research and the many different roles that serendipity has played in the collaborations that are described herein.

Description: This article discusses experimental observation of carrier-envelope-phase effects by multicycle pulses. Abstract: We present an experimental and theoretical study of carrier-envelope-phase (CEP) effects on the population transfer between two bound atomic states interacting with pulses consisting of many cycles. Using intense radio-frequency pulse with Rabi frequency of the order of the atomic transition frequency, the authors investigate the influence of the CEP on the control of phase-dependent multiphoton transitions between the Zeeman sublevels of the ground state of ⁸⁷Rb. Our scheme has no limitation on the duration of the pulses. Extending the CEP control to longer pulses creates interesting possibilities to generate pulses with accuracy that is better than the period of optical oscillations.

Description: This article discusses isomerization reactions of bidentate phosphine ligands in triosmium clusters. Abstract: The diphosphine ligand 1,2-bis(diphenylphosphino) benzene (dppbz) reacts with the activated cluster 1,2-Os3 (CO)10 (MeCN)2 (1) at room temperature to furnish a mixture of the triosmium clusters 1,2-Os3 (CO)10 (dppbz) (2) and 1,1-Os3 (CO)10 (dppbz) (3), along with a trace amount of the hydride cluster HOs3 (CO)9 [μ -1,2-PhP (C6H4-ɳ1) C6H4PPh2] (4). The dppbz-bridged cluster 2 forms as the kinetically controlled product and irreversibly transforms to the corresponding chelated isomer 3 at ambient temperature. The disposition of the dppbz ligand in 2 and 3 has been established by X-ray crystallography and 31P NMR spectroscopy, and the kinetics for the conversion 2 → 3 have been followed by UV-vis spectroscopy in toluene over the temperature range 318-343 K. The calculated activation parameters (ΔH‡ = 21.6(3)kcal/mol; ΔS‡ = -11(1)eu) and lack of CO inhibition support an intramolecular isomerization mechanism that involves the simultaneous migration of phosphine and CO groups about the cluster polyhedron. The reaction between 1 and the fluorinated diphosphine ligand 1,2-bis(diphenylphosphino) tetrafluorobenzene (dppbzF4) was examined under similar reaction conditions and was found to afford the chelated cluster 1,1-Os3 (CO)10 (dppbzF4) (6) as the sole observable product. The absence ...

Description: This article discusses photoelectron spectroscopic study of the oxyallyl diradical. The photoelectron spectrum of the oxyallyl (OXA) radical anion has been measured. The radical anion has been generated in the reaction of the atomic oxygen radical anion (O߭߫) with acetone. Three low-lying electronic states of OXA have been observed in the spectrum. Electronic structure calculations have been performed for the triplet states (3B2 and 3B1) of OXA and the ground doublet state (2A2) of the radical anion using density functional theory (DFT). Spectral simulations have been carried out for the triplet states based on the results of the DFT calculations. The simulations identifies a vibrational progression of the CCC bending mode of the 3B2 state of OXA in the lower electron binding energy (eBE) portion of the spectrum. On top of the 3B2 feature, however, the experimental spectrum exhibits additional photo-electron peaks whose angular distribution is distinct from that for the vibronic peaks of the 3B2 state. Complete active space self-consistent field (CASSCF) method and second-order perturbation theory based on the CASSCF wave function (CASPT2) have been employed to study the lowest singlet state (1A1) of OXA. The simulation based on the results of these electronic structure calculations establishes that ...

Description: This article discusses correlation of solute transfer into toluene and ethylbenzene from water and from the gas phase based on the Abraham model. Experimental data have been compiled from the published literature on the partition coefficients of solutes and vapors into ethylbenzene and toluene at 298 K. The logarithms of the water-to-ethylbenzene and water-to-toluene partition coefficients, log P, and gas-to-ehtylbenzene and gas-to-toluene partition coefficients, log K, were correlated with the Abraham solvation parameter model. The derived mathematical expressions described the observed log P and log K data for the two aromatic hydrocarbon solvents to within average deviations of 0.13 log units or less.