729 research outputs found
QCD Pressure and the Trace Anomaly
Exact relations between the QCD thermal pressure and the trace anomaly are
derived. These are used, first, to prove the equivalence of the thermodynamic
and the hydrodynamic pressure in equilibrium in the presence of the trace
anomaly, closing a gap in previous arguments. Second, in the temporal axial
gauge a formula is derived which expresses the thermal pressure in terms of a
Dyson-resummed two-point function. This overcomes the infrared problems
encountered in the conventional perturbation-theory approach.Comment: 9 pages plain te
Observation and ultrafast dynamics of a nonvalence correlation-bound state of an anion
Nonvalence states of molecular anions play key roles in processes, such as electron mobility, in rare-gas liquids, radiation-induced damage to DNA, and the formation of anions in the interstellar medium. Recently, a class of nonvalence bound anion state has been predicted by theory in which correlation forces are predominantly responsible for binding the excess electron. We present a direct spectroscopic observation of this nonvalence correlation-bound state (CBS) in the para-toluquinone trimer cluster anion. Time-resolved photoelectron velocity map imaging shows that photodetachment of the CBS produces a narrow and highly anisotropic photoelectron distribution, consistent with detachment from an s-like orbital. The CBS is bound by ~50 meV and decays by vibration-mediated autodetachment with a lifetime of 700 ± 100 fs. These states are likely to be common in large and/or polarizable anions and clusters and may act as doorway states in electron attachment processes
Fingerprinting the Excited State Dynamics in Methyl Ester and Methyl Ether Anions of Deprotonated para-Coumaric Acid
Chromophores based on the para-hydroxycinnamate moiety are widespread in the natural world, including as the photoswitching unit in photoactive yellow protein and as a sunscreen in the leaves of plants. Here, photodetachment action spectroscopy combined with frequency- and angle-resolved photoelectron imaging is used to fingerprint the excited state dynamics over the first three bright action-absorption bands in the methyl ester anions (pCEsâ) of deprotonated para-coumaric acid at a temperature of â300K. The excited states associated with the action- absorption bands are classified as resonances because they are situated in the detachment continuum and are open to autodetachment. The frequency-resolved photoelectron spectrum for pCEsâ indicates that all photon energies over the S1(ÏÏâ) band lead to similar vibrational autodetachment dynamics. The S2(nÏâ) band is Herzberg-Teller active and has comparable brightness to the higher lying 21(ÏÏâ) band. The frequency-resolved photoelectron spectrum over the S2(nÏâ) band indicates more efficient internal conversion to the S1(ÏÏâ) state for photon energies resonant with the Franck-Condon modes (â80 %) compared with the Herzberg-Teller modes (â60%). The third action-absorption band, which corresponds to excitation of the 21(ÏÏâ) state, shows com- plex and photon-energy-dependent dynamics, with 20â40% of photoexcited population internally converting to the S1(ÏÏâ) state. There is also evidence for a mode-specific competition between prompt autodetachment and internal conversion on the red edge of the 21(ÏÏâ) band. There is no evidence for recovery of the ground elec- tronic state and statistical electron ejection (thermionic emission) following photoexcitation over any of the three action-absorption bands. Photoelectron spectra for the deprotonated methyl ether derivative (pCEtâ) at photon energies over the S1(ÏÏâ) and S2(nÏâ) bands indicate diametrically opposed dynamics compared with pCEsâ, namely intense thermionic emission due to efficient recovery of the ground electronic state
Ultrafast valence to non-valence excited state dynamics in a common anionic chromophore
Non-valence states in neutral molecules (Rydberg states) have well-established roles and importance in photochemistry, however, considerably less is known about the role of non-valence states in photo-induced processes in anions. Here, femtosecond time-resolved photoelectron imaging is used to show that photoexcitation of the S1(ÏÏ*) state of the methyl ester of deprotonated para-coumaric acid â a model chromophore for photoactive yellow protein (PYP) â leads to a bifurcation of the excited state wavepacket. One part remains on the S1(ÏÏ*) state forming a twisted intermediate, whilst a second part leads to the formation of a non-valence (dipole-bound) state. Both populations eventually decay independently by vibrational autodetachment. Valence-to-non-valence internal conversion has hitherto not been observed in the intramolecular photophysics of an isolated anion, raising questions into how common such processes might be, given that many anionic chromophores have bright valence states near the detachment threshold
NMR Determination of Oligonucleotide Structure
This unit provides an overview of the use of NMR to determine oligonucleotide structure. It covers basic NMR spectral properties, acquisition of interproton distance restraints and torsion angle restraints, structure refinement, assessment of the quality of the structure obtained. Software programs used in the process are also described.Peer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/143742/1/cpnc0702.pd
Ultrafast photoisomerisation of an isolated retinoid
The photoinduced excited state dynamics of gas-phase trans-retinoate (deprotonated trans-retinoic acid, trans-RAâ) are studied using tandem ion mobility spectrometry coupled with laser spectroscopy, and frequency-, angle- and time-resolved photoelectron imaging. Photoexcitation of the bright S3(ÏÏ*) â S0 transition leads to internal conversion to the S1(ÏÏ*) state on a â80 fs timescale followed by recovery of S0 and concomitant isomerisation to give the 13-cis (major) and 9-cis (minor) photoisomers on a â180 fs timescale. The sub-200 fs stereoselective photoisomerisation parallels that for the retinal protonated Schiff base chromophore in bacteriorhodopsin. Measurements on trans-RAâ in methanol using the solution photoisomerisation action spectroscopy technique show that 13-cis-RAâ is also the principal photoisomer, although the 13-cis and 9-cis photoisomers are formed with an inverted branching ratio with photon energy in methanol when compared with the gas phase, presumably due to solvent-induced modification of potential energy surfaces and inhibition of electron detachment processes. Comparison of the gas-phase time-resolved data with transient absorption spectroscopy measurements on retinoic acid in methanol suggest that photoisomerisation is roughly six times slower in solution. This work provides clear evidence that solvation significantly affects the photoisomerisation dynamics of retinoid molecules
Short period line profile and light variations in the Be star Ï Orionis
We present the results of a multisite spectroscopic and photometric campaign on the Be star Ï Orionis. From the photometry and radial velocity variation of several spectral lines, we confirm that the star is a variable with period . Only one period can be extracted from both the photometric and radial velocity observations. We find that the projected rotational velocity from the helium lines is considerably smaller than from the metal lines . The line profiles show an excess absorption feature moving from blue to red for half the period and from red to blue for the other half of the period. Another excess absorption feature moves exactly out of phase. The excess absorption features are present in photospheric lines as well as in lines which are significantly affected by circumstellar material, such as HÎČ. From this we conclude that the periodic variations are most probably associated with corotating circumstellar materia
The Isgur-Wise function in a relativistic model for system
We use the Dirac equation with a ``(asymptotically free) Coulomb + (Lorentz
scalar) linear '' potential to estimate the light quark wavefunction for mesons in the limit . We use these wavefunctions to
calculate the Isgur-Wise function for orbital and radial
ground states in the phenomenologically interesting range . We find a simple expression for the zero-recoil slope, , where is the energy eigenvalue
of the light quark, which can be identified with the parameter
of the Heavy Quark Effective Theory. This result implies an upper bound of
for the slope . Also, because for a very light quark the size of the meson is determined mainly by the
``confining'' term in the potential , the shape of
is seen to be mostly sensitive to the dimensionless
ratio . We present results for the ranges of
parameters , and
light quark masses and compare to existing
experimental data and other theoretical estimates. Fits to the data give:
,
and [ARGUS
'93]; , and
[CLEO '93]; ${\bar\Lambda_{u,d}}^2/Comment: 22 pages, Latex, 4 figures (not included) available by fax or via
email upon reques
The fossil record of early tetrapods: worker effort and the end-Permian mass extinction
It is important to understand the quality of the fossil record of early tetrapods (Tetrapoda, minus Lissamphibia and Amniota) because of their key role in the transition of vertebrates from water to land, their dominance of terrestrial faunas for over 100 million years of the late Palaeozoic and earlyMesozoic, and their variable fates during the endâPermian mass extinction. The first description of an early tetrapod dates back to 1824, and since then discoveries have occurred at a rather irregular pace, with peaks and troughs corresponding to some of the vicissitudes of human history through the past two centuries. As expected, the record is dominated by the wellâsampled sedimentary basins of Europe and North America, but finds from other continents are increasing rapidly. Comparisons of snapshots of knowledge in 1900, 1950, and 2000 show that discovery of new species has changed the shape of the speciesâlevel diversification curve, contrary to earlier studies of familyâlevel taxa. There is, however, little evidence that taxon counts relate to research effort (as counted by numbers of publications), and there are no biasing effects associated with differential study of different time intervals through the late Palaeozoic and Mesozoic. In fact, levels of effort are apparently not related to geological time, with no evidence that workers have spent more time on more recent parts of the record. In particular, the endâPermian mass extinction was investigated to determine whether diversity changes through that interval might reflect worker effort: it turns out that most records of early tetrapod taxa (when corrected for duration of geological series) occur in the Lower Triassic
Nonadiabatic Dynamics between Valence, Nonvalence, and Continuum Electronic States in a Heteropolycyclic Aromatic Hydrocarbon
Internal conversion between valence-localized and dipole-bound states is thought to be a ubiquitous process in polar molecular anions, yet there is limited direct evidence. Here, photodetachment action spectroscopy and time-resolved photoelectron imaging with a heteropolycyclic aromatic hydrocarbon (hetero-PAH) anion, deprotonated 1-pyrenol, is used to demonstrate a subpicosecond (Ï1 = 160 ± 20 fs) valence to dipole-bound state internal conversion following excitation of the origin transition of the first valence-localized excited state. The internal conversion dynamics are evident in the photoelectron spectra and in the photoelectron angular distributions (ÎČ2 values) as the electronic character of the excited state population changes from valence to nonvalence. The dipole-bound state subsequently decays through mode-specific vibrational autodetachment with a lifetime Ï2 = 11 ± 2 ps. These internal conversion and autodetachment dynamics are likely common in molecular anions but difficult to fingerprint due to the transient existence of the dipole-bound state. Potential implications of the present excited state dynamics for interstellar hetero-PAH anion formation are discussed
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