Effect of OH internal torsion on the OH-stretching spectrum of cis,cis-HOONO

We show that a simple two-dimensional vibrational model can explain most of the features observed in the first and second OH-stretching overtone region of the room temperature cis,cis-HOONO spectrum. The model uses ab initio calculated parameters and includes the OH-stretching mode coupled to the internal torsion of the OH group.     

Solar Thermal Energy Storage in a Photochromic Macrocycle

The conversion and efficient storage of solar energy is recognized to hold significant potential with regard to future energy solutions. Molecular solar thermal batteries based on photochromic systems exemplify one possible technology able to harness and apply this potential. Herein is described the synthesis of a macrocycle based on a dimer of the dihydroazulene/vinylheptafulvene (DHA/VHF) photo/thermal couple. By taking advantage of conformational strain, this DHA–DHA macrocycle presents an improved ability to absorb and store incident light energy in chemical bonds (VHF–VHF). A stepwise energy release over two sequential ring‐closing reactions (VHF→DHA) combines the advantages of an initially fast discharge, hypothetically addressing immediate energy consumption needs, followed by a slow process for consistent, long‐term use. This exemplifies another step forward in the molecular engineering and design of functional organic materials towards solar thermal energy storage and release.     

Measurement of ultraweak transitions in the visible region of molecular oxygen

A highly sensitive cavity-enhanced frequency modulation spectroscopy technique has been used to measure ultraweak transitions in molecular oxygen that had not previously been characterized. The self-broadened half-width and line intensity of the measured transitions are reported. We include 12 high J transitions in the band of ¹⁶O₂ (the so-called A band), 59 transitions in the hot band of ¹⁶O₂, and 17 high J transitions in the band of ¹⁶O¹⁸O. Our measurements of line positions of the ¹⁶O¹⁸O transitions are used to determine improved molecular constants for the excited state of ¹⁶O¹⁸O.     

Imaging of s and d partial-wave interference in quantum scattering of identical bosonic atoms

We report on the direct imaging of s and d partial-wave interference in cold collisions of atoms. Two ultracold clouds of 87Rb atoms were accelerated by magnetic fields to collide at energies near a d-wave shape resonance. The resulting halos of scattered particles were imaged using laser absorption. By scanning across the resonance we observed a marked evolution of the scattering patterns due to the energy dependent phase shifts for the interfering s and d waves. Since only two partial-wave states are involved in the collision process the scattering yield and angular distributions have a simple interpretation in terms of a theoretical model.     

Peroxy radical isomerization in the oxidation of isoprene

We report experimental evidence for the formation of C(5)-hydroperoxyaldehydes (HPALDs) from 1,6-H-shift isomerizations in peroxy radicals formed from the hydroxyl radical (OH) oxidation of 2-methyl-1,3-butadiene (isoprene). At 295 K, the isomerization rate of isoprene peroxy radicals (ISO2?) relative to the rate of reaction of ISO2? + HO2 is k(isom)(295)/(k(ISO2?+HO2)(295)) = (1.2 ± 0.6) x 10(8) mol cm(-3), or k(isom)(295) ? 0.002 s(-1). The temperature dependence of this rate was determined through experiments conducted at 295, 310 and 318 K and is well described by k(isom)(T)/(k(ISO2?+HO2)(T)) = 2.0 x 10(21) exp(-9000/T) mol cm(-3). The overall uncertainty in the isomerization rate (relative to k(ISO2?+HO2)) is estimated to be 50%. Peroxy radicals from the oxidation of the fully deuterated isoprene analog isomerize at a rate ～15 times slower than non-deuterated isoprene. The fraction of isoprene peroxy radicals reacting by 1,6-H-shift isomerization is estimated to be 8-11% globally, with values up to 20% in tropical regions.     

OH-stretch vibrational spectroscopy of hydroxymethyl hydroperoxide

We report measurement and analysis of the photodissociation spectrum of hydroxymethyl hydroperoxide (HOCH(2)OOH) and its partially deuterated analogue, HOCD(2)OOH, in the OH-stretching region. Spectra are obtained by Fourier transform infrared spectroscopy in the 1nu(OH) and 2nu(OH) regions, and by laser induced fluorescence detection of the OH fragment produced from dissociation of HOCH(2)OOH initiated by excitation of the 4nu(OH) and 5nu(OH) overtone regions (action spectroscopy). A one-dimensional local-mode model of each OH chromophore is used with ab initio calculated OH-stretching potential energy and dipole moment curves at the coupled-cluster level of theory. Major features in the observed absorption and photodissociation spectra are explained by our local-mode model. In the 4nu(OH) region, explanation of the photodissocation spectrum requires a nonuniform quantum yield, which is estimated by assuming statistical energy distribution in the excited state. Based on the estimated dissociation threshold, overtone photodissociation is not expected to significantly influence the atmospheric lifetime of hydroxymethyl hydroperoxide.     

Calculated electronic transitions in sulfuric acid and implications for its photodissociation in the atmosphere

We have calculated electronic transitions for sulfuric acid in the ultraviolet region using a hierarchy of coupled cluster response functions and correlation consistent basis sets. Our calculations indicate that the lowest energy singlet transition occurs at 8.42 eV with an oscillator strength of 0.01. The lowest energy triplet state occurs at 8.24 eV. Thus, the cross section of sulfuric acid in the actinic region is likely to be very small and smaller than the upper limit put on this cross section by previous experimental investigations. We estimate the cross section of sulfuric acid in the atmospherically relevant Lyman-alpha region ( approximately 10.2 eV) to be approximately 6 x 10 (-17) cm (2) molecule (-1), a value approximately 30 times larger than the speculative value used in previous atmospheric simulations. We have calculated the J values for photodissociation of sulfuric acid with absorption of visible, UV, and Lyman-alpha radiation, at altitudes between 30 and 100 km. We find that the dominant photodissociation mechanism of sulfuric acid below 70 km is absorption in the visible region by OH stretching overtone transitions, whereas above 70 km, absorption of Lyman-alpha radiation by high energy Rydberg excited states is the favored mechanism. The low lying electronic transitions of sulfuric acid in the UV region do not contribute significantly to its dissociation at any altitude.     

Vibrational overtone spectroscopy of three-membered rings

We have recorded vapor-phase photoacoustic spectra of cyclopropane, ethylene oxide, and ethylene sulfide in the third, fourth, and fifth CH-stretching overtone regions. We have used a harmonically coupled anharmonic oscillator local mode model to facilitate analysis of the spectra. Fermi resonance between the CH-stretching and HCH-bending vibrations is essential to explain the observed wide and multistructured CH-stretching overtone bands. A number of weak combination bands can account for the remaining experimental features observed to the blue of the CH-stretching regions. We have reassigned the fundamental spectra of these three-membered rings.     

Vibrational OH-stretching overtone spectroscopy of jet-cooled resorcinol and hydroquinone rotamers

We have measured the OH-stretching fundamental and overtone spectra of resorcinol and hydroquinone in a supersonic jet using nonresonant ionization detected infrared/near-infrared spectroscopy. Anharmonic oscillator local mode calculations of the OH-stretching frequencies and intensities and Boltzmann populations of the stable rotamers have been calculated at the B3LYP/6-311++G(3df,2pd) level to help interpret the observed spectra. Resorcinol has three stable rotamers and in the recorded second and third OH-stretching overtone spectra there is evidence of two distinguishable rotamers. Hydroquinone has two stable rotamers; however, the OH-stretching oscillators of each rotamer are so similar in nature that even up to the fourth OH-stretching overtone the transitions coincide. These results place a limit on the ability of the jet-cooled overtone spectroscopy technique to distinguish between rotamers.     

The lowest 2A' excited state of the water-hydroxyl complex

Vertical and adiabatic excitation energies of the lowest (2)A(') excited state in the water-hydroxyl complex have been determined using coupled cluster, multireference configuration interaction, multireference perturbation theory, and density-functional methods. A significant redshift of about 0.4 eV in the vertical excitation energy of the complex compared to that of the hydroxyl radical monomer is found with the coupled cluster calculations validating previous results. Electronic excitation leads to a structure with near-equal sharing of the hydroxyl hydrogen by both oxygen atoms and a concomitantly large redshift of the adiabatic excitation energy of approximately 1 eV relative to the vertical excitation energy. The combination of redshifts ensures that the electronic transition in the complex lies well outside the equivalent excitation in the hydroxyl radical monomer. The complex is approximately five times more strongly bound in the excited state than in the ground state.