The Role of Strain in the Homoaromatization of Semibullvalenes.

The low activation barrier to the Cope rearrangement of semibullvalenes has been attributed to the inherent ring-strain of this nucleus. Appropriate, Dewar-Hoffmann, substitution of semibullvalene results in the stabilization of the transition state and a further lowering of the Cope barrier. An alternative proposal for lowering/eliminating this barrier is the use of strain to destabilize the localized semibullvalene. Using density functional and Hartree-Fock calculations, we predict that additionally straining the semibullvalene nucleus, by small ring annelations, will lead to a lowering of the Cope barrier and ultimately to ground state neutral homoaromatics.

Broadband interferometric characterization of divergence and spatial chirp.

We demonstrate a spectral interferometric method to characterize lateral and angular spatial chirp to optimize intensity localization in spatio-temporally focused ultrafast beams. Interference between two spatially sheared beams in an interferometer will lead to straight fringes if the wavefronts are curved. To produce reference fringes, we delay one arm relative to another in order to measure fringe rotation in the spatially resolved spectral interferogram. With Fourier analysis, we can obtain frequency-resolved divergence. In another arrangement, we spatially flip one beam relative to the other, which allows the frequency-dependent beamlet direction (angular spatial chirp) to be measured. Blocking one beam shows the spatial variation of the beamlet position with frequency (i.e., the lateral spatial chirp).

Nonlinear dynamics of double-pass cross-polarized wave generation in the saturation regime.

The conversion efficiency of cross-polarized wave (XPW) generation can be improved using two separate thinner nonlinear crystals versus a single thick one, due to the evolution of the beam sizes and individual phases after the first crystal. In this paper, we present an alternative scheme in which a curved mirror is used to reimage a plane just after the BaF2 crystal for a second pass. We also develop a simple analytic model for XPW conversion that describes the origin of a nonlinear phase mismatch and nonlinear lensing for both the fundamental wave and XPW. Coupled with the numerical solution for the process and the Fresnel propagation after the first pass, we also explore the factors that affect the efficiency of saturated, seeded XPW conversion. These include the development of the on-axis relative phase difference in the first crystal and after it (during free-space propagation), mode matching, wavefront curvature difference, and crystal tuning angle. We also experimentally demonstrate that the beam quality of the XPW signal after the second pass can be improved by the reimaging.

Spatial-spectral characterization of focused spatially chirped broadband laser beams.

Proper alignment is critical to obtain the desired performance from focused spatially chirped beams, for example in simultaneous spatial and temporal focusing (SSTF). We present a simple technique for inspecting the beam paths and focusing conditions for the spectral components of a broadband beam. We spectrally resolve the light transmitted past a knife edge as it was scanned across the beam at several axial positions. The measurement yields information about spot size, M2, and the propagation paths of different frequency components. We also present calculations to illustrate the effects of defocus aberration on SSTF beams.

Measurement of energy contrast of amplified ultrashort pulses using cross-polarized wave generation and spectral interferometry.

We present a method using spectral interferometry (SI) to characterize a pulse in the presence of an incoherent background such as amplified spontaneous emission (ASE). The output of a regenerative amplifier is interfered with a copy of the pulse that has been converted using third-order cross-polarized wave generation (XPW). The ASE shows as a pedestal background in the interference pattern. The energy contrast between the short-pulse component and the ASE is retrieved. The spectra of the interacting beams are obtained through an improvement to the self-referenced spectral interferometry (SRSI) analysis.