N-H center dot center dot center dot pi hydrogen-bonding and large-amplitude tipping vibrations in jet-cooled pyrrole-benzene

The N-H center dot center dot center dot pi hydrogen bond is an important intermolecular interaction in many biological systems. We have investigated the infrared (IR) and ultraviolet (UV) spectra of the supersonic-jet cooled complex of pyrrole with benzene and benzene-d(6) (Pyr center dot Bz, Pyr center dot Bz-d(6)). DFT-D density functional, SCS-MP2 and SCS-CC2 calculations predict a T-shaped and (almost) C(s) symmetric structure with an N-H center dot center dot center dot pi hydrogen bond to the benzene ring. The pyrrole is tipped by omega(S(0)) = +/- 13 degrees relative to the surface normal of Bz. The N center dot center dot center dot ring distance is 3.13 angstrom. In the S(1) excited state, SCS-CC2 calculations predict an increased tipping angle omega(S(1)) = +/- 21 degrees. The IR depletion spectra support the T-shaped geometry: The NH stretch is redshifted by -59 cm(-1), relative to the "free" NH stretch of pyrrole at 3531 cm(-1), indicating a moderately strong N-H center dot center dot center dot pi interaction. The interaction is weaker than in the (Pyr)(2) dimer, where the NH donor shift is -87 cm(-1) [Dauster et al., Phys. Chem. Chem. Phys., 2008, 10, 2827]. The IR C-H stretch frequencies and intensities of the Bz subunit are very similar to those of the acceptor in the (Bz)(2) dimer, confirming that Bz acts as the acceptor. While the S(1) <- S(0) electronic origin of Bz is forbidden and is not observable in the gas-phase, the UV spectrum of Pyr center dot Bz in the same region exhibits a weak 0(0)(0) band that is red-shifted by 58 cm(-1) relative to that of Bz (38 086 cm(-1)). The origin appears due to symmetry-breaking of the p-electron system of Bz by the asymmetric pyrrole NH center dot center dot center dot pi hydrogen bond. This contrasts with (Bz)(2), which does not exhibit a 0(0)(0) band. The Bz moiety in Pyr center dot Bz exhibits a 6a(0)(1) band at 0(0)(0) + 518 cm(-1) that is about 20x more intense than the origin band. The symmetry breaking by the NH center dot center dot center dot pi hydrogen bond splits the degeneracy of the v(6)(e(2g)) vibration, giving rise to 6a' and 6b' sub-bands that are spaced by similar to 6 cm(-1). Both the 0(0)(0) and 6(0)(1) bands of Pyr center dot Bz carry a progression in the low-frequency (10 cm(-1)) excited-state tipping vibration omega', in agreement with the change of the omega tipping angle predicted by SCS-MP2 and SCS-CC2 calculations.

Search for Quantum Black Hole Production in High-Invariant-Mass Lepton plus Jet Final States Using pp Collisions at root s=8 TeV and the ATLAS Detector

This Letter presents a search for quantum black-hole production using 20.3 fb(-1) of data collected with the ATLAS detector in pp collisions at the LHC at root s = 8 TeV. The quantum black holes are assumed to decay into a final state characterized by a lepton (electron or muon) and a jet. In either channel, no event with a lepton-jet invariant mass of 3.5 TeV or more is observed, consistent with the expected background. Limits are set on the product of cross sections and branching fractions for the lepton + jet final states of quantum black holes produced in a search region for invariant masses above 1 TeV. The combined 95% confidence level upper limit on this product for quantum black holes with threshold mass above 3.5 TeV is 0.18 fb. This limit constrains the threshold quantum black-hole mass to be above 5.3 TeV in the model considered.

Measurement of inclusive jet charged-particle fragmentation functions in Pb+Pb collisions at √sNN = 2.76 TeV with the ATLAS detector

Measurements of charged-particle fragmentation functions of jets produced in ultra-relativistic nuclear collisions can provide insight into the modification of parton showers in the hot, dense medium created in the collisions. ATLAS has measured jets in √sNN=2.76 TeV Pb+Pb collisions at the LHC using a data set recorded in 2011 with an integrated luminosity of 0.14 nb−1. Jets were reconstructed using the anti-kt algorithm with distance parameter values R = 0.2, 0.3, and 0.4. Distributions of charged-particle transverse momentum and longitudinal momentum fraction are reported for seven bins in collision centrality for R=0.4 jets with pjetT>100 GeV. Commensurate minimum pT values are used for the other radii. Ratios of fragment distributions in each centrality bin to those measured in the most peripheral bin are presented. These ratios show a reduction of fragment yield in central collisions relative to peripheral collisions at intermediate z values, 0.04≲z≲0.2 and an enhancement in fragment yield for z≲0.04. A smaller, less significant enhancement is observed at large z and large pT in central collisions.