Spectroscopy Of Hydrogen-bonded Formanilide Clusters In A Supersonic Jet: Solvation Of A Model Trans Amide

The gas-phase structures of trans-formanilide (FA) clusters containing varying numbers of water and ammonia molecules have been investigated by resonant two-photon ionization spectroscopy in a supersonic jet expansion. A single structure is found for the 1:1 cluster of FA with ammonia in which the amide NH group functions as a hydrogen bond donor to the ammonia nitrogen. In contrast, vibronically resolved spectra reveal two distinct structures for the 1:1 cluster with water in which either the amide NH group functions as a hydrogen bond donor or the carbonyl oxygen functions as a hydrogen bond acceptor. The 1:1 clusters with both ammonia and water exhibit characteristic spectral shifts that depend on which amide site participates in the hydrogen bond. Three distinct types of 1:2 clusters with water have been found. Two of these can be viewed as water dimers interacting through a single hydrogen bond with either the amide NH group or the carbonyl oxygen. The third structure involves a hydrogen bond at each amide site to a separate water molecule. Ternary FA clusters containing one ammonia and one water molecule have also been investigated and found to be present in two distinct structural forms. Although each structure contains a hydrogen bond between the amide NH and one of the solvents, the structures differ with regard to which solvent serves as the acceptor of this hydrogen bond as well as in the role of the second solvent. Finally, clusters containing four water molecules have been identified, although in this case only a single cluster structure has been observed. This species is assigned to a structure containing a hydrogen-bonded chain of four water molecules forming a bridge between the NH and carbonyl oxygen binding sites on opposite sides of the trans amide. These experimental observations and structural assignment are supported by ab initio Hartree-Fock calculations

Electronic Spectroscopy of Jet-Cooled Benzylidenecyclobutane, a Sterically Hindered Styrene

The electronic spectrum of the styrene derivative, benzylidenecyclobutane, seeded in a supersonic jet expansion has been recorded using resonantly enhanced two-photon ionization spectroscopy. The main vibronic features in the spectrum are associated with a low frequency progression assigned to the torsional motion of the phenyl ring. Analysis of the observed torsional levels reveals an excited state potential energy surface characteristic of a planar equilibrium geometry which undergoes large amplitude motion and a ground state surface having a minimum at a torsional angle of 25° between the phenyl and vinyl groups. Ab initio calculations of the ground state torsional potential surface predict a minimum in the range of 28°-26°, depending on the size of the basis set. In these structures the cyclobutane ring adopts a puckering angle between 17° and 19°. Deuterated isotopomers have also been synthesized and their corresponding photoionization spectra analyzed to reveal the mixing between the torsion and other low frequency modes such as cyclobutane ring puckering. The extent of this mixing is found to be sensitive to the sites of deuteration on the molecule. © 1996 American Institute of Physics

Electronic Spectroscopy of Jet-Cooled Benzylidenecyclobutane, a Sterically Hindered Styrene

The electronic spectrum of the styrene derivative, benzylidenecyclobutane, seeded in a supersonic jet expansion has been recorded using resonantly enhanced two-photon ionization spectroscopy. The main vibronic features in the spectrum are associated with a low frequency progression assigned to the torsional motion of the phenyl ring. Analysis of the observed torsional levels reveals an excited state potential energy surface characteristic of a planar equilibrium geometry which undergoes large amplitude motion and a ground state surface having a minimum at a torsional angle of 25° between the phenyl and vinyl groups. Ab initio calculations of the ground state torsional potential surface predict a minimum in the range of 28°-26°, depending on the size of the basis set. In these structures the cyclobutane ring adopts a puckering angle between 17° and 19°. Deuterated isotopomers have also been synthesized and their corresponding photoionization spectra analyzed to reveal the mixing between the torsion and other low frequency modes such as cyclobutane ring puckering. The extent of this mixing is found to be sensitive to the sites of deuteration on the molecule. © 1996 American Institute of Physics

Conformations And Relative Stabilities Of The Cis And Trans Isomers In A Series Of Isolated N-phenylamides

The gas-phase conformations of a series of isolated N-phenylamides have been determined from vibrationally resolved electronic spectra obtained by resonant two-photon ionization in a supersonic jet expansion. Both the cis and trans isomers of formanilide were identified, with the cis isomer in 6.5% abundance. The spectral features displayed by this isomer are consistent with a nonplanar geometry which undergoes a large change in the phenyl torsional angle following electronic excitation. The more abundant trans isomer of formanilide adopts a planar structure and is stabilized by 2.5 kcal/mol with respect to the cis isomer. In the excited electronic state the relative stabilities of the two isomers are reversed. Acetanilide, in contrast, is found exclusively as the trans isomer, also having a planar structure. N-Methyl substitution causes a reversal of the relative isomer stabilities found in formanilide and leads to an isomer distribution consisting of approximately 90% E and 10% Z in N-methylformanilide. These experimental observations are compared to previous condensed phase structural determinations as well as to the relative energies and structures predicted from ab initio Hartree-Fock geometry optimizations

Invariant quantum discord in qubit-qutrit systems under local dephasing

We investigate the dynamics of quantum discord and entanglement for a class of mixed qubit-qutrit states assuming that only the qutrit is under the action of a dephasing channel. We demonstrate that even though the entanglement in the qubit-qutrit state disappears in a finite time interval, partial coherence left in the system enables quantum discord to remain invariant throughout the whole time evolution

Infrared Spectroscopy of H-Bonded Bridges Stretched across the cis-Amide Group: II. Ammonia and Mixed Ammonia/Water Bridges

Clusters of two model cis amides, oxindole and 3,4-dihydro-2(IH)-quinolinone, containing one and two ammonia molecules have been studied in the IR hydride stretch region using resonant ion-dip IR spectroscopy. The spectra confirm that ammonia is able to form hydrogen-bonded bridges across the adjacent amide N-H and C=O sites in a manner very similar to that of water. Such bridged structures require that ammonia assume the role of a hydrogen bond donor. Further similarities of the hydrogen bonding capabilities of ammonia and water have been revealed by investigations of ternary clusters containing an amide, one ammonia, and one water molecule. Experimentally, two species are observed having IR spectra consistent with a hydrogen-bonded bridge structure. The two species differ only in the relative positions of the ammonia and water molecules within the bridge. These experimental results are well supported by optimized structures, vibrational frequencies, and IR intensities calculated using density functional theory with the Becke3LYP functional. Additionally, the characteristic features of the hydride stretch fundamentals in a hydrogen-bond-donating ammonia molecule can be readily understood using a simple model for the coupled NH oscillators in which the hydrogen-bonded NH has its force constant lowered and its dipole derivative increased, much like in other hydrogen-bonded XH groups

Infrared Spectroscopy Of H-bonded Bridges Stretched Across The Cis-amide Group: I. Water Bridges

The water-containing clusters of oxindole (OI) and 3,4-dihydro-2(1H)-quinolinone (DQ) have been studied in the hydride stretch region of the infrared by the technique of resonant ion-dip infrared spectroscopy (RIDIRS). Both OI and DQ are constrained cis-amides with adjacent N-H and C=O groups between which water can form H-bonded bridges. The hydride stretch fundamentals of OI-W-n with n = 1-3 and DQ-W-n with n = 1, 2 without exception divide up into free OH stretch fundamentals near 3700 cm(-1) and a set of H-bonded bridge fundamentals in the 3200-3450 cm(-1) region. The bridge fundamentals show a distribution of intensities that reflects strong coupling among the XH oscillators in the bridge. When more than one water is involved in the bridge, the bridge fundamentals are unusually broad, with widths of 50-80 cm(-1) full width at half-maximum. Minimum-energy structures, binding energies, vibrational frequencies, and infrared intensities have been calculated by density functional theory with a Becke3LYP functional and a 6-31+G* basis set. The calculated infrared spectra match experiment well, confirming the bridge structures for the clusters. The form of the calculated normal modes provides insight into the nature of the bridge fundamentals

Getting into hot water:sick guppies frequent warmer thermal conditions

Ectotherms depend on the environmental temperature for thermoregulation and exploit thermal regimes that optimise physiological functioning. They may also frequent warmer conditions to up-regulate their immune response against parasite infection and/or impede parasite development. This adaptive response, known as ‘behavioural fever’, has been documented in various taxa including insects, reptiles and fish, but only in response to endoparasite infections. Here, a choice chamber experiment was used to investigate the thermal preferences of a tropical freshwater fish, the Trinidadian guppy (Poecilia reticulata), when infected with a common helminth ectoparasite Gyrodactylus turnbulli, in female-only and mixed-sex shoals. The temperature tolerance of G. turnbulli was also investigated by monitoring parasite population trajectories on guppies maintained at a continuous 18, 24 or 32 °C. Regardless of shoal composition, infected fish frequented the 32 °C choice chamber more often than when uninfected, significantly increasing their mean temperature preference. Parasites maintained continuously at 32 °C decreased to extinction within 3 days, whereas mean parasite abundance increased on hosts incubated at 18 and 24 °C. We show for the first time that gyrodactylid-infected fish have a preference for warmer waters and speculate that sick fish exploit the upper thermal tolerances of their parasites to self medicate

Quantum correlations in a few-atom spin-1 Bose-Hubbard model

We study the thermal quantum correlations and entanglement in spin-1 Bose-Hubbard model with two and three particles. While we use negativity to calculate entanglement, more general non-classical correlations are quantified using a new measure based on a necessary and sufficient condition for zero-discord state. We demonstrate that the energy level crossings in the ground state of the system are signalled by both the behavior of thermal quantum correlations and entanglement

Decoherence on a two-dimensional quantum walk using four- and two-state particle

We study the decoherence effects originating from state flipping and depolarization for two-dimensional discrete-time quantum walks using four-state and two-state particles. By quantifying the quantum correlations between the particle and position degree of freedom and between the two spatial ($x-y$) degrees of freedom using measurement induced disturbance (MID), we show that the two schemes using a two-state particle are more robust against decoherence than the Grover walk, which uses a four-state particle. We also show that the symmetries which hold for two-state quantum walks breakdown for the Grover walk, adding to the various other advantages of using two-state particles over four-state particles.Comment: 12 pages, 16 figures, In Press, J. Phys. A: Math. Theor. (2013