Improved semiempirical heats of formation through the use of bond and group equivalents

Deficiencies in energetics obtained using the common semiempirical methods, AM1, PM3, and MNDO, may partly be traced to the use of pseudoatomic equivalents for conversion of molecular energies to heats of formation at 298 K. We present an alternative scheme based on the use of bond and group equivalents. Values for the 61 bond and group equivalents necessary for treatment of molecules containing the common organic elements, hydrogen, carbon, nitrogen, and oxygen have been derived. For a set of 583 neutral, closed-shell molecules mean absolute errors in AM1, PM3, and MNDO heats of formation are reduced from 6.6, 4.2, and 8.2 kcal/mol to 2.3, 2.2, and 3.0 kcal/mol, respectively. Several systematic problems are overcome in the present scheme including relative stabilities of branched hydrocarbons, energetics of conjugated systems, heats of formation of long chain hydrocarbons, and enthalpies of molecules containing multiple heteroatoms. Although the approach is restricted to molecules with well-defined functional groups, the equivalents are easy to incorporate and are chemically relevant. This revised procedure allows semiempirical methods to be used for far more reliable evaluations of heats of reactions. Estimates are made of the errors inherent in these semiempirical formalisms, arising from integral approximations and the neglect of explicit treatment of electron correlation effects, while excluding those from inadequate parameterization.     

High-conversion-efficiency, diode-pumped continuous-wave Raman laser

We demonstrate a diode-pumped cw Raman laser in H(2) with photon-conversion efficiency of (66+/-8)%. Pumped by an injection-locked diode laser at 792 nm, the Stokes laser produces a peak output power of ~16mW at 1180 nm. Accompanying the high Stokes power are deviations from the existing theory, which are believed to be caused by the thermal-lensing effect of the Raman gas.     

Widely tunable continuous-wave Raman laser in diatomic hydrogen pumped by an external-cavity diode laser

What is to the authors' knowledge the first experimental demonstration of a nonresonant cw Raman laser pumped by a tunable external-cavity diode laser (ECDL) is presented. The ECDL is phase-frequency locked to a high-finesse Raman laser cavity containing diatomic hydrogen (H(2)) by the Pound-Drever-Hall locking technique. The Stokes lasing threshold occurs at a pump power of 400 +/- 30 muW, and a maximum photon conversion efficiency of 12.0 +/- 1.3% is achieved at 1.6 mW of pump power. A 40-nm tuning range of the cw Stokes emission, 1174-1214 nm, is obtained by tuning of the wavelength of the ECDL pump source.     

Accumulated programming of a complex spectral grating

A complex spectral grating is accumulated by repeated application of a pair of low-power optical programming pulses to a short-term persistent inhomogeneously broadened transition in Tm:YAG at 4.5 K and then probed to investigate the buildup dynamics. The necessary frequency stability is obtained by locking a cw Ti:sapphire laser to a regenerating transient spectral hole in the same transition. Grating accumulation is demonstrated for both a periodic spectral grating, representing a true-time delay, and a complex spectral grating, permitting correlation-based pattern recognition. This work is a step toward demonstrating an optical coherent transient continuously programmed continuous processor.     

Continuous-wave Raman laser in H(2)

Recent developments in high-finesse cavities now make broadly tunable, continuous-wave Raman lasers possible. The design and preliminary characterization of what is to the authors' knowledge the first continuous-wave Raman laser in H(2) are presented. The threshold is currently at 2 mW of pump, making diode laser pumping possible. The maximum photon conversion efficiency observed was 35% at 7.6 mW of pump power.     

Conservative methods for the Toda lattice equations

We are concerned with the numerical integration of the Todalattice equations by using different conservative methods. Numericalexperiments suggest that the global error for isospectral schemesdecreases exponentially with time but it is almost constantfor either symplectic or more general integrators. We providea theoretical explanation for these experimental findings.