Effects of partially quenched orbital angular momentum on the microwave spectrum and magnetic hyperfine splitting in the OH–water complex

Brauer, Carolyn S.; Sedo, Galen; Grumstrup, Erik M.; Leopold, K. R.; Marshall, Mark D.; Leung, Helen O.

doi:10.1016/j.cplett.2004.11.090

Cited by 58 publications

(70 citation statements)

References 31 publications

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“…4 is very similar to that calculated by Ohshima et al, 14 with a hydrogen bond length of 1.910 Â 10 À10 m. Our calculated bond length can also be compared with that obtained by Brauer et al 15 via an analysis of their Fourier transform microwave spectrum, 1.952 Â 10 À10 m. The latter quantity should, of course, be larger because of vibrational averaging over the anharmonic stretching motion, and also because the very low lying A 00 state, for which we compute a CCSD(T) hydrogen bond length of 1.938 Â 10 À10 m, may be significantly populated. The CBS extrapolation employed here eliminates any influence of basis set superposition error on the energy, which would lead to overestimated binding energies for theoretical methods based on moderate-sized basis sets.…”

Section: (B) Computational Resultssupporting

confidence: 90%

“…The binding enthalpy at 298.15 K, D r H 298. 15 , was obtained via enthalpy corrections based on the computed frequencies (assuming harmonic behaviour) and the experimental spin-orbit splittings noted above.…”

Section: (A) Ab Initio Calculations On the Hydrogen-bonded H 2 O-ho Smentioning

confidence: 99%

“…Recently, there have been two reports 14,15 of the observation of the H 2 O-HO hydrogen-bonded species by gas-phase rotational spectroscopy. In addition, there have been two reports 16 of the infrared spectrum of H 2 OÀHO in solid argon matrices, as well as investigations 17 of the potential energy surface for H 2 O-HO using photoelectron spectroscopy.…”

Section: Introductionmentioning

confidence: 99%

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The relaxation of OH (v = 1) and OD (v = 1) by H2O and D2O at temperatures from 251 to 390 K

McCabe

Rajakumar

Marshall

et al. 2006

Phys. Chem. Chem. Phys.

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We report rate coefficients for the relaxation of OH(v = 1) and OD(v = 1) by H 2 O and D 2 O as a function of temperature between 251 and 390 K. All four rate coefficients exhibit a negative dependence on temperature. In Arrhenius form, the rate coefficients for relaxation (in units of 10 À12 cm 3 molecule À1 s À1 ) can be expressed as: for OH ( , 1977, 66, 4758), in order to estimate the rates of intramolecular energy transfer from the OH (OD) vibration to other modes in the complexes in order to explain the measured relaxation rates-assuming that relaxation proceeds via the hydrogen-bonded complexes.

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Section: (B) Computational Resultssupporting

confidence: 90%

Section: (A) Ab Initio Calculations On the Hydrogen-bonded H 2 O-ho Smentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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The relaxation of OH (v = 1) and OD (v = 1) by H2O and D2O at temperatures from 251 to 390 K

McCabe

Rajakumar

Marshall

et al. 2006

Phys. Chem. Chem. Phys.

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“…The observed band structure shown in Fig. 3 was more faithfully reproduced, however, by including a spin-rotation interaction to account for the effects of electronic state mixing in the open-shell species; this effect has been demonstrated previously in high-resolution studies of the OH-water complex (16)(17)(18). The resultant rotational band simulation shown in Fig.…”

Section: Resultsmentioning

confidence: 71%

Spectroscopic identification and stability of the intermediate in the OH + HONO ₂ reaction

O’Donnell

Lester

et al. 2008

Proc. Natl. Acad. Sci. U.S.A.

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The reaction of nitric acid with the hydroxyl radical influences the residence time of HONO2 in the lower atmosphere. Prior studies [Brown SS, Burkholder JB, Talukdar RK, Ravishankara AR (2001) J Phys Chem A 105:1605-1614] have revealed unusual kinetic behavior for this reaction, including a negative temperature dependence, a complex pressure dependence, and an overall reaction rate strongly affected by isotopic substitution. This behavior suggested that the reaction occurs through an intermediate, theoretically predicted to be a hydrogen-bonded OH-HONO2 complex in a six-membered ring-like configuration. In this study, the intermediate is generated directly by the association of photolytically generated OH radicals with HONO2 and stabilized in a pulsed supersonic expansion. Infrared action spectroscopy is used to identify the intermediate by the OH radical stretch ( 1) and OH stretch of nitric acid ( 2) in the OH-HONO2 complex. Two vibrational features are attributed to OH-HONO2: a rotationally structured 1 band at 3516.8 cm ؊1 and an extensively broadened 2 feature at 3260 cm ؊1 , both shifted from their respective monomers. These same transitions are identified for OD-DONO 2. Assignments of the features are based on their vibrational frequencies, analysis of rotational band structure, and comparison with complementary high level ab initio calculations. In addition, the OH (v ‫؍‬ 0) product state distributions resulting from 1 and 2 excitation are used to determine the binding energy of OH-HONO2, D0 < 5.3 kcal⅐mol ؊1 , which is in good accord with ab initio predictions.atmospheric chemistry ͉ hydroxyl radical ͉ nitric acid ͉ reaction intermediate N itric acid is a chemically inactive and photochemically stable reservoir for reactive HO x and NO x species in the atmosphere. In the troposphere, HONO 2 is usually removed by dry deposition or rainout faster than it is photochemically converted back to NO x , making it a permanent sink for NO x (1, 2). In the upper troposphere and stratosphere, where there is no rain, HONO 2 can be removed by solar photolysis and reaction with OH (3, 4),This reaction results in the conversion of HONO 2 into reactive NO x species, because the unstable nitrate radical rapidly decomposes into NO or NO 2 .Kinetic studies have shown that the OH ϩ HONO 2 reaction is unusual in several respects (3, 5-11), particularly under the temperature and pressure conditions found in the lower atmosphere. Under these conditions, this reaction exhibits a negative temperature dependence, a pressure dependence, and a strong kinetic isotope effect. The indirect mechanism inferred from these studies consists of initial OH radical addition forming an energized OH-HONO 2 * intermediate, followed by redissociation or reaction to form products. The energized intermediate can also be temporarily stabilized by collisions with bath gas M, and then redissociate to reactants or decompose to products as shown in the following scheme:The unusual kinetic behavior arises because of enhanced formation and collisional st...

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“…In the atmosphere of Earth, open-shell radical species, although present in small concentrations, are important intermediates in chemical reactions. Recent laboratory and theoretical work highlighted the properties of radical complexes with water with potentially significant chemical effects in the atmosphere (34)(35)(36)(37)47). In the D region of Earth's atmosphere, hydrated molecular clusters such as the protonated water cluster H 3 O ϩ (H 2 O) n have been observed (17,(19)(20)(21)(22).…”

mentioning

confidence: 99%

Molecular complexes in close and far away

Klemperèr

Vaida

2006

Proc. Natl. Acad. Sci. U.S.A.

110

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In this review, gas-phase chemistry of interstellar media and some planetary atmospheres is extended to include molecular complexes. Although the composition, density, and temperature of the environments discussed are very different, molecular complexes have recently been considered as potential contributors to chemistry. The complexes reviewed include strongly bound aggregates of molecules with ions, intermediate-strength hydrogen bonded complexes (primarily hydrates), and weakly bonded van der Waals molecules. In low-density, low-temperature environments characteristic of giant molecular clouds, molecular synthesis, known to involve gas-phase ion-molecule reactions and chemistry at the surface of dust and ice grains is extended here to involve molecular ionic clusters. At the high density and high temperatures found on planetary atmospheres, molecular complexes contribute to both atmospheric chemistry and climate. Using the observational, laboratory, and theoretical database, the role of molecular complexes in close and far away is discussed.P lanetary atmospheres and interstellar media have traditionally been lumped together; they are complex dynamical entities whose understanding has been and continues to be a challenge. That this subject is new may be appreciated by the fact that the knowledge that hydrogen is the abundant element of the universe is less than 100 years old. Hydrogen and helium comprise more than 99% of the universe. Thus, interstellar chemistry must be quite different from that of the atmospheres of the minor planets Mars, Earth, and Venus. Conceding the dominance of hydrogen and helium on the cosmic scale and even in the major planets, more complex molecules than H 2 attract our attention and dominate our thinking (1-4).An understanding of the chemistry of the universe must involve a wide range of processes. A bit of history with respect to interstellar chemistry is relevant to our perspective. The observed interstellar molecules, CH, CH ϩ , and CN, are quantitatively discussed by Herbig (5) in his classic study of z Oph. These species have optical transitions in spectral regions where Earth's atmosphere is transparent. It was assumed that in interstellar clouds, which were translucent and thus bathed in the galactic radiation field, the major components were atomic. Because the average density of the galaxy is 1 atom cm Ϫ1 (6) three-body processes were readily dismissed. Kramers and ter Haar (7) in 1946 presented a calculation for the formation of CH by the radiative association of C and H, i.e., C ϩ H ϭ CH ϩ photon. In 1951 Bates and Spitzer (8) showed that the CH calculated formation rate was seriously incorrect and with that ruled out synthesis by gas-phase association. Their concluding statement ushered in a lengthy period with emphasis on molecular synthesis on grain surfaces under a variety of conditions (3,(9)(10)(11).With the advent of molecular radioastronomy (12) the molecular character of giant molecular clouds could be examined. These are the largest structures within the gala...

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Effects of partially quenched orbital angular momentum on the microwave spectrum and magnetic hyperfine splitting in the OH–water complex

Cited by 58 publications

References 31 publications

The relaxation of OH (v = 1) and OD (v = 1) by H2O and D2O at temperatures from 251 to 390 K

The relaxation of OH (v = 1) and OD (v = 1) by H2O and D2O at temperatures from 251 to 390 K

Spectroscopic identification and stability of the intermediate in the OH + HONO ₂ reaction

Molecular complexes in close and far away

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Effects of partially quenched orbital angular momentum on the microwave spectrum and magnetic hyperfine splitting in the OH–water complex

Cited by 58 publications

References 31 publications

The relaxation of OH (v = 1) and OD (v = 1) by H2O and D2O at temperatures from 251 to 390 K

The relaxation of OH (v = 1) and OD (v = 1) by H2O and D2O at temperatures from 251 to 390 K

Spectroscopic identification and stability of the intermediate in the OH + HONO 2 reaction

Molecular complexes in close and far away

Contact Info

Product

Resources

About

Spectroscopic identification and stability of the intermediate in the OH + HONO ₂ reaction