Unraveling the internal dynamics of the benzene dimer: a combined theoretical and microwave spectroscopy study

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Observing the First Stars and Black Holes

The high sensitivity of JWST will open a new window on the end of the cosmological dark ages. Small stellar clusters, with a stellar mass of several 10^6 M_sun, and low-mass black holes (BHs), with a mass of several 10^5 M_sun should be directly detectable out to redshift z=10, and individual supernovae (SNe) and gamma ray burst (GRB) afterglows are bright enough to be visible beyond this redshift. Dense primordial gas, in the process of collapsing from large scales to form protogalaxies, may also be possible to image through diffuse recombination line emission, possibly even before stars or BHs are formed. In this article, I discuss the key physical processes that are expected to have determined the sizes of the first star-clusters and black holes, and the prospect of studying these objects by direct detections with JWST and with other instruments. The direct light emitted by the very first stellar clusters and intermediate-mass black holes at z>10 will likely fall below JWST's detection threshold. However, JWST could reveal a decline at the faint-end of the high-redshift luminosity function, and thereby shed light on radiative and other feedback effects that operate at these early epochs. JWST will also have the sensitivity to detect individual SNe from beyond z=10. In a dedicated survey lasting for several weeks, thousands of SNe could be detected at z>6, with a redshift distribution extending to the formation of the very first stars at z>15. Using these SNe as tracers may be the only method to map out the earliest stages of the cosmic star-formation history. Finally, we point out that studying the earliest objects at high redshift will also offer a new window on the primordial power spectrum, on 100 times smaller scales than probed by current large-scale structure data.Comment: Invited contribution to "Astrophysics in the Next Decade: JWST and Concurrent Facilities", Astrophysics & Space Science Library, Eds. H. Thronson, A. Tielens, M. Stiavelli, Springer: Dordrecht (2008

An ab initio study of the rotation—vibration energy levels of GeH2 in the X̃1A1 state

Thirty-seven points on the potential-energy surface of the X̃1A1 ground electronic state for the GeH2 radical have been calculated using the (ab initio) MRD Cl technique. Twelve parameters in an analytic expression for the potential have been adjusted (by least-squares optimization) so that the surface fits these points. The rotation—vibration energy levels of GeH2 and GeD2 have been calculated using the non-rigid bender Hamiltonian, and we determine for GeH2 that ν1 = 1857 cm−1, ν2 = 923 cm−1 and ν3 = 1866 cm−1, in good agreement with the values obtained from a matrix-isolation spectrum. The equilibrium structure is found to be re = 1.591 A and αe = 91.4°

Ab initio rotation-vibration energies and intensities for the H2F+ molecule

In a previous publication [I. D. Petsalakis, G. Theodorakopoulos, J. S. Wright, and I. P. Hamilton, J. Chem. Phys., 92, 2440-2449 (1990)] we reported the ab initio multireference configuration interaction calculation of the three-dimensional potential energy surface of the H2F+ molecule in the ground X ̃1A1 electronic state at 119 nuclear geometries spanning an energy range up to about 50 000 cm-1 above equilibrium. We fitted the 71 points within 33 000 cm-1 of equilibrium to an analytic expression and performed variational calculation of the vibrational energies in Jacobi coordinates using the Discrete Variable Representation and Distributed Gaussian Basis functions (DVR-DGB) technique. In the present paper we examine the effect on the vibrational energies of using a surface obtained by fitting through 52 points within 25 000 cm-1 of equilibrium. We use this surface in a variational calculation of the J = 0, 1, and 2 rotation-vibration energies using the Morse Oscillator Rigid Bender Internal Dynamics Hamiltonian [P. Jensen, J. Mol. Spectrosc., 128, 478-501 (1988); J. Chem. Soc. Faraday Trans. 2, 84, 1315-1340 (1988)]. The vibrational energies obtained are compared with those obtained by the DVR-DGB technique. We also calculate ab initio the dipole moment function and rotation-vibration intensities, and we simulate the ν2 band, which has not yet been observed