Gas-Phase Clustering of NO+ with H2S and H2O

2007 ◽  
Vol 72 (8) ◽  
pp. 1122-1138 ◽  
Author(s):  
Milan Uhlár ◽  
Ivan Černušák
Keyword(s):  
Hydrogen Bonds ◽  
Water Molecule ◽  
Gas Phase ◽  
Saddle Points ◽  
Solvent Molecule ◽  
Local Minima ◽  
Additional Water ◽  
Three Body ◽  
Rain Formation ◽  
Stable Structures

The complex NO+·H2S, which is assumed to be an intermediate in acid rain formation, exhibits thermodynamic stability of ∆Hº300 = -76 kJ mol-1, or ∆Gº300 = -47 kJ mol-1. Its further transformation via H-transfer is associated with rather high barriers. One of the conceivable routes to lower the energy of the transition state is the action of additional solvent molecule(s) that can mediate proton transfer. We have studied several NO+·H2S structures with one or two additional water molecule(s) and have found stable structures (local minima), intermediates and saddle points for the three-body NO+·H2S·H2O and four-body NO+·H2S·(H2O)2 clusters. The hydrogen bonds network in the four-body cluster plays a crucial role in its conversion to thionitrous acid.

Komplexe mit substituierten 2,5-Dihydroxy-p-benzochinonen: EA[C6(NO2)2O4] · H2O (EA = Ca, Sr)/ Complexes with Substituted 2,5-D ihydroxy-p-benzoquinones: EA [C6(NO2)2O4] · 4H2O(EA = Ca, Sr)

1987 ◽  
Vol 42 (8) ◽  
pp. 972-976 ◽  
Author(s):  
Christian Robl
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bonds ◽  
Water Molecule ◽  
Single Crystals ◽  
Coordination Sphere ◽  
Trigonal Prism ◽  
Water Molecules ◽  
Additional Water ◽  
Oxygen Atoms

AbstractSingle crystals of EA[Q(NO2)2O4] · 4H2O (EA = Ca. Sr) were grown in aqueous silicagel. Ca2+ has CN 8. It is surrounded by 4 oxygen atoms of two bis-chelating [C6(NO2)2O4]2- ions and 4 water molecules, which form a distorted, bi-capped trigonal prism. Sr2+ is coordinated similarly, with an additional water molecule joining the coordination sphere to yield CN 8+1. Corrugated chains extending along [010] and consisting of EA2+ and nitranilate ions are the main feature of the crystal structure. Adjacent chains are interlinked by hydrogen bonds.

scholarly journals VERY LOW H–O–H BENDING FREQUENCIES. VI. VIBRATIONAL SPECTRA OF CdCl2·H2O

2017 ◽  
Vol 38 (1) ◽  
pp. 91
Author(s):  
Viktor Stefov ◽  
Metodija Najdoski ◽  
Bernward Engelen ◽  
Zlatko Ilievski ◽  
Adnan Cahil
Keyword(s):  
Hydrogen Bonds ◽  
Water Molecule ◽  
Gas Phase ◽  
Raman Spectra ◽  
Structural Data ◽  
Liquid Nitrogen Temperature ◽  
Water Molecules ◽  
Deuterium Content ◽  
Infrared And Raman Spectra ◽  
The Difference

The infrared and Raman spectra of CdCl2·H2O as well as those of a series of its partially deuterated analogues were recorded at room and at liquid-nitrogen temperature (RT and LNT, respectively). The combined results from the analysis of the spectra were used to assign the observed bands. In the difference IR spectrum of the compound with low deuterium content (≈ 4 % D) recorded at RT, one broad bands is observed at around 2590 cm–1 while in the LNT spectrum two bands appear (at 2584 cm–1 and 2575 cm–1). The appearance in the LNT spectrum of these two bands which are due to the stretching OD modes of the isotopically isolated HDO molecules points to the existance of two crystallographically different hydrogen bonds and is in accordance with the structural data for this compound. In the LNT infrared and Raman spectra of the protiated compound, one band, at 1583 cm-1, is observed in the region of the bending НОН vibrations with a frequency that is decreasing with lowering the temperature. An interesting finding related to this band is that its frequency is lower than that for the water molecule in the gas phase (1594 cm–1). In the RT and LNT IR spectra, only one strong band (at 560 cm–1) is observed in the region of the librations of water molecules (700 cm–1 – 400 cm–1).

scholarly journals Bis(3,5-di-tert-butyl-4H-1,2,4-triazol-4-amine-κN 1)(nitrato-κO)silver(I) ethanol monosolvate monohydrate

2012 ◽  
Vol 68 (6) ◽  
pp. m731-m731
Author(s):  
Ya-Mei Liu ◽  
Jing-Huo Chen ◽  
Guang Yang ◽  
Seik Weng Ng
Keyword(s):  
Hydrogen Bond ◽  
Hydrogen Bonds ◽  
Water Molecule ◽  
Lattice Water Molecule ◽  
Solvent Molecule ◽  
Coordination Geometry ◽  
Hydrogen Bond Donor ◽  
Hydrogen Bond Acceptor ◽  
Lattice Water ◽  
Linear Coordination

The AgI atom in the title compound, [Ag(NO3)(C10H20N4)2]·C2H5OH·H2O, is coordinated by the N atoms of two N-heterocycles [N—Ag—N = 151.5 (1)°]; the approximately linear coordination geometry is distorted into a T-shaped geometry owing to a long Ag...Onitrate bond [2.717 (4) Å]. The N atoms of the N-heterocycles that are not involved in coordination point towards the lattice water molecule, which functions as a hydrogen-bond donor. The water molecule itself is a hydrogen-bond acceptor towards the ethanol solvent molecule. Hydrogen bonds of the type N–H...O give rise to a layer motif parallel to (001).

scholarly journals N-[2-(2,2-Dimethylpropanamido)pyrimidin-4-yl]-2,2-dimethylpropanamiden-hexane 0.25-solvate hemihydrate

2013 ◽  
Vol 69 (11) ◽  
pp. o1617-o1618
Author(s):  
Borys Ośmiałowski ◽  
Arto Valkonen ◽  
Lilianna Chęcińska
Keyword(s):  
Hydrogen Bonds ◽  
Water Molecule ◽  
Title Compound ◽  
Solvent Molecule ◽  
Inversion Center ◽  
Asymmetric Unit ◽  
Compound C ◽  
Independent Molecules

The asymmetric unit of the title compound, C14H22N4O2·0.25C6H14·0.5H2O, contains two independent molecules of 2,4-bis(pivaloylamino)pyrimidine (M) with similar conformations, one water molecule and one-halfn-hexane solvent molecule situated on an inversion center. In one independentMmolecule, one of the twotert-butyl groups is rotationally disordered between two orientations in a 3:2 ratio. Then-hexane solvent molecule is disordered between two conformations in the same ratio. The water molecule bridges two independentMmoleculesviaO—H...O, N—H...O and O—H...N hydrogen bonds into a 2M·H2O unit, and these units are further linked by N—H...N hydrogen bonds into chains running in the [010] direction. Weak C—H...O interactions are observed between the adjacent chains.

Geometrical and vibrational DFT studies of HOBr·(H2O)n clusters (n = 1–4)

2003 ◽  
Vol 81 (9) ◽  
pp. 961-970 ◽  
Author(s):  
Cristina Maria P Santos ◽  
Roberto B Faria ◽  
Wagner B De Almeida ◽  
Juan O Machuca-Herrera ◽  
Sérgio P Machado
Keyword(s):  
Binding Energy ◽  
Hydrogen Bonds ◽  
Water Molecule ◽  
Vibrational Spectra ◽  
Low Frequency ◽  
Binding Energies ◽  
Basis Sets ◽  
Dft Studies ◽  
Geometrical Structures ◽  
Stable Structures

The geometrical structures and the vibrational spectra of the HOBr·(H2O)n clusters (n = 1–4) have been calculated at the DFT level of theory, using the pBP method and the DN* and DN** numerical basis sets. The results showed that the interaction involving the H of the HOBr and the O of the water molecule represent the preferred arrangements for these hydrated compounds. Both HOBr·H2O and HOBr·(H2O)2 clusters presented stable structures with syn and anti conformations, the syn being the most stable. The HOBr·(H2O)3 and the HOBr·(H2O)4 clusters have presented stable cyclic structures. In the HOBr·H2O and HOBr·(H2O)2 clusters, low-frequency stretching values could be assigned to hydrogen bonds, but the same could not be done so clearly for the HOBr·(H2O)3 and the HOBr·(H2O)4 cyclic clusters. The binding energies were also determinated for these HOBr hydrated clusters, showing that the addition of a water molecule to the HOBr·H2O and HOBr·(H2O)2 clusters increases the binding energy by approximately 4 kcal mol–1, while the addition of a water molecule to the HOBr·(H2O)3 cluster decreases this value by 4 kcal mol–1.Key words: DFT, numerical basis, HOBr·(H2O)n, clusters.

Theoretical study of the hydrolysis of HOSO+NO2 as a source of atmospheric HONO: effects of H2O or NH3

2017 ◽  
Vol 14 (1) ◽  
pp. 19 ◽  
Author(s):  
Yan-Qiu Sun ◽  
Xu Wang ◽  
Feng-Yang Bai ◽  
Xiu-Mei Pan
Keyword(s):  
Hydrogen Bonds ◽  
Water Molecule ◽  
Ion Pairs ◽  
Ammonia Molecule ◽  
Main Reaction ◽  
Energy Structure ◽  
Atmospheric Pollutant ◽  
Additional Water ◽  
Effective Role ◽  
Hydrolysis Of

Environmental contextNitrous acid (HONO) has long been recognized as an important atmospheric pollutant, with the reaction of HOSO+NO2 being a source of HONO. We explore the effects of an additional water or ammonia molecule on this reaction. Calculations show that the ammonia molecule has a more effective role than the water molecule in assisting the reaction. AbstractDepending on different ways that NO2 approaches the HOSO radical, the main reactant complexes HOS(O)NO2 and HOS(O)ONO–L (lowest energy structure of the isomer) were revealed by Lesar et al. (J. Phys. Chem. A 2011, 115, 11008), and the reaction of HOSO+NO2 is a source of trans (t)-HONO and SO2. In the present work, the water molecule in the hydrolysis reaction of HOSO+NO2 not only acts as a catalyst giving the products of t-HONO+SO2, but also as a reactant giving the products of t-HONO+H2SO3, c-HONO+H2SO3 and HNO3+t-S(OH)2. For the reaction of HOSO+NO2+H2O, the main reaction paths 2, 7, and 9 are further investigated with an additional water or ammonia molecule. The CBS-QB3 calculation result shows that the process of HOS(O)NO2–H2O → t-HONO–SO2–H2O is favourable with a barrier of 0.1kcal mol–1. Although the following process of t-HONO–SO2–H2O → t-HONO–H2SO3 is unfavourable with a barrier 33.6kcal mol–1, the barrier is reduced by 17.3 or 26.3kcal mol–1 with an additional water or ammonia molecule. Starting with HOS(O)ONO–L–H2O, the energy barriers of path 7 and path 9 are reduced by 8.9 and 8.5kcal mol–1 with an additional water molecule and by 9.9 and 9.2kcal mol–1 with an additional ammonia molecule. Ammonia is more beneficial than water for assisting the HOSO+NO2+H2O reaction. Three t-HONO–H2SO3 isomers which contain double intermolecular hydrogen bonds are studied by frequency and natural bond orbital calculations. Frequency calculations show that all hydrogen bonds exhibit an obvious red shift. The larger second-order stabilisation energies are consistent with the shorter hydrogen bonds. H2SO3 can promote the process of t-HONO → HNO2, and reduce the barrier by 45.2kcal mol–1. The product NH3–H2SO3 can further form a larger cluster (NH3–H2SO3)n (n=2, 4) including NH4+HSO3– ion pairs.

Computational study on the deamination reaction of adenine with OH−/nH2O (n = 0, 1, 2, 3) and 3H2O

2013 ◽  
Vol 91 (7) ◽  
pp. 518-526 ◽  
Author(s):  
Ahmad I. Alrawashdeh ◽  
Mansour H. Almatarneh ◽  
Raymond A. Poirier
Keyword(s):  
Activation Energy ◽  
Water Molecule ◽  
Gas Phase ◽  
Activation Barrier ◽  
Computational Study ◽  
Polarizable Continuum Model ◽  
Intrinsic Reaction Coordinate ◽  
Rate Determining Step ◽  
Additional Water ◽  
Deamination Reaction

Deamination of adenine is one of several forms of premutagenic lesions occurring in DNA. In the present study, mechanisms for the deamination reaction of adenine with OH−/nH2O (n = 0, 1, 2, 3) and 3H2O were investigated. HF/6-31G(d), B3LYP/6-31G(d), MP2/6-31G(d), and B3LYP/6-31+G(d) levels of theory were employed to search for and optimize all geometries. Energies were calculated at the G3MP2B3 and CBS-QB3 levels of theory. The effect of solvent (water) was computed using the polarizable continuum model (PCM). Intrinsic reaction coordinate (IRC) calculations were performed for all transition states. Five pathways were investigated for the deamination reaction of adenine with OH−/nH2O and 3H2O. The first four pathways (A–D) are initiated by deprotonation at the amino group of adenine by OH−, while pathway E is initiated by tautomerization of adenine. For all pathways the next two steps involve formation of a tetrahedral intermediate followed by dissociation to products via a 1,3-proton shift. Deamination with a single OH− has a high activation barrier (190 kJ mol−1 using the G3MP2B3 level) for the rate-determining step. The addition of one water molecule reduces this barrier by 68 kJ mol−1 at the G3MP2B3 level. Adding additional water molecules decreases the overall activation energy of the reaction, but the effect becomes smaller with each additional water molecule. The most plausible mechanism is pathway E, the deamination reaction of adenine with 3H2O, with an overall G3MP2B3 activation energy of 139 and 137 kJ mol−1 for the gas phase and PCM, respectively. This barrier is lower than that for the deamination with OH−/3H2O by 6 and 2 kJ mol−1 for the gas phase and PCM, respectively.

A Crystallographic Study of Bis[S-benzyl-5-bromo-2-oxoindolin-3-ylidenemethanehydrazonthioate] Disulfide Solvated with Dimethylsulfoxide

2012 ◽  
Vol 9 (2) ◽  
pp. 87
Author(s):  
Mohd Abdul Fatah Abdul Manan ◽  
M. Ibrahim M. Tahir ◽  
Karen A. Crouse ◽  
Fiona N.-F. How ◽  
David J. Watkin
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bonds ◽  
Solvent Molecule ◽  
Site Occupancy ◽  
Unit Cell Parameters ◽  
Intermolecular Hydrogen Bonds ◽  
Triclinic Space Group ◽  
Cell Parameters ◽  
Crystallographic Study ◽  
Thiol Form

The crystal structure of the title compound has been determined. The compound crystallized in the triclinic space group P -1, Z = 2, V = 1839 .42( 18) A3 and unit cell parameters a= 11. 0460( 6) A, b = 13 .3180(7) A, c=13. 7321 (8) A, a = 80.659(3 )0, b = 69 .800(3 )0 and g = 77 .007 (2)0 with one disordered dimethylsulfoxide solvent molecule with the sulfur and oxygen atoms are distributed over two sites; S101/S102 [site occupancy factors: 0.6035/0.3965] and 0130/0131 [site occupancy factor 0.3965/0.6035]. The C22-S2 l and C 19-S20 bond distances of 1. 779(7) A and 1. 788(8) A indicate that both of the molecules are connected by the disulfide bond [S20-S21 2.055(2) A] in its thiol form. The crystal structure reveals that both of the 5-bromoisatin moieties are trans with respect to the [S21-S20 and CI 9-Nl 8] and [S20-S21 and C22-N23] bonds whereas the benzyl group from the dithiocarbazate are in the cis configuration with respect to [S21-S20 and C19-S44] and [S20-S21 and C22-S36] bonds. The crystal structure is further stabilized by intermolecular hydrogen bonds of N9-H35···O16 formed between the two molecules and N28-H281 ···O130, N28-H281 ···O131 and C4 l-H4 l l ···O 131 with the solvent molecule.

scholarly journals Cyclooctanaminium hydrogen succinate monohydrate

2012 ◽  
Vol 68 (4) ◽  
pp. o1204-o1204 ◽  
Author(s):  
Sanaz Khorasani ◽  
Manuel A. Fernandes
Keyword(s):  
Hydrogen Bonds ◽  
Water Molecule ◽  
Ammonium Cation ◽  
Water Molecules ◽  
Hydrated Salt ◽  
A Chain ◽  
Hydrogen Bonded

In the title hydrated salt, C8H18N+·C4H5O4−·H2O, the cyclooctyl ring of the cation is disordered over two positions in a 0.833 (3):0.167 (3) ratio. The structure contains various O—H.·O and N—H...O interactions, forming a hydrogen-bonded layer of molecules perpendicular to thecaxis. In each layer, the ammonium cation hydrogen bonds to two hydrogen succinate anions and one water molecule. Each hydrogen succinate anion hydrogen bonds to neighbouring anions, forming a chain of molecules along thebaxis. In addition, each hydrogen succinate anion hydrogen bonds to two water molecules and the ammonium cation.

scholarly journals Piperazinium hydrogenarsenate monohydrate

2007 ◽  
Vol 63 (3) ◽  
pp. m905-m907 ◽  
Author(s):  
Hazel S. Wilkinson ◽  
William T. A. Harrison
Keyword(s):  
Hydrogen Bonds ◽  
Water Molecule ◽  
Title Compound ◽  
Water Molecules ◽  
Asymmetric Unit ◽  
Compound C

In the title compound, C4H12N2 2+·HAsO4 2−·H2O, the component species interact by way of N—H...O and O—H...O hydrogen bonds, the latter leading to infinite sheets of HAsO4 2− anions and water molecules containing R 6 6(18) loops. The asymmetric unit contains one anion, one water molecule and half each of two centrosymmetric cations.

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