Breaking symmetry with hydrogen bonds: Vibrational predissociation and isomerization dynamics in HF–DF and DF–HF isotopomers

1996 ◽  
Vol 104 (23) ◽  
pp. 9313-9331 ◽  
Author(s):  
John T. Farrell ◽  
Martin A. Suhm ◽  
David J. Nesbitt
Keyword(s):  
Hydrogen Bonds ◽  
Vibrational Predissociation ◽  
Breaking Symmetry

Symmetry of hydrogen bonds in solution

2009 ◽  
Vol 81 (4) ◽  
pp. 571-583 ◽  
Author(s):  
Charles L. Perrin
Keyword(s):  
Hydrogen Bonds ◽  
Local Environment ◽  
Deuterium Isotope Effect ◽  
Wide Range ◽  
The Asymmetry ◽  
Catalyzed Reactions ◽  
Enzyme Catalyzed Reactions ◽  
Breaking Symmetry ◽  
C Nmr

A classic question regarding hydrogen bonds (H-bonds) concerns their symmetry. Is the hydrogen centered or is it closer to one donor and jumping between them? These possibilities correspond to single- and double-well potentials, respectively. The NMR method of isotopic perturbation can answer this question. It is illustrated with 3-hydroxy-2-phenylpropenal and then applied to dicarboxylate monoanions. The 18O-induced 13C NMR splittings signify that their intramolecular H-bonds are asymmetric and that each species is a pair of tautomers, not a single symmetric structure, even though maleate and phthalate are symmetric in crystals. The asymmetry is seen across a wide range of solvents and a wide variety of monoanions, including 2,3-di-tert-butylsuccinate and zwitterionic phthalates. Asymmetry is also seen in monoprotonated 1,8-bis(dimethylamino)naphthalenediamines, N,N'-diaryl-6-aminofulvene-2-aldimines, and 6-hydroxy-2-formylfulvene. The asymmetry is attributed to the disorder of the local environment, establishing an equilibrium between solvatomers. The broader implications of these results regarding the role of solvation in breaking symmetry are discussed. It was prudent to confirm a secondary deuterium isotope effect (IE) on amine basicity by NMR titration of a mixture of PhCH2NH2 and PhCHDNH2. The IE is of stereoelectronic origin. It is proposed that symmetric H-bonds can be observed in crystals but not in solution because a disordered environment induces asymmetry, whereas a crystal can guarantee a symmetric environment. The implications for the controversial role of low-barrier H-bonds in enzyme-catalyzed reactions are discussed.

Use of molecular overlap to predict intermolecular repulsion in N... H-O hydrogen bonds

1998 ◽  
Vol 95 (3) ◽  
pp. 525-537 ◽  
Author(s):  
I. NOBELI S. L. PRICE R. J. WHEATLEY
Keyword(s):  
Hydrogen Bonds

On symmetrical O-H-O hydrogen bonds

1964 ◽  
Vol 25 (5) ◽  
pp. 487-492 ◽  
Author(s):  
R.E. Rundle
Keyword(s):  
Hydrogen Bonds

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.

Molecular Characterization of the Surface Excess Charge Layer in Droplets

2020 ◽  
Author(s):  
Victor Kwan ◽  
Styliani Consta
Keyword(s):  
Hydrogen Bonds ◽  
Surface Charge ◽  
Droplet Size ◽  
Chloride Ions ◽  
Total Charge ◽  
Excess Charge ◽  
Surface Excess ◽  
High Concentration ◽  
Dipole Orientation ◽  
Charge Layer

<div>Charged droplets play a central role in native mass spectrometry, atmospheric aerosols and in serving as micro-reactors for accelerating chemical reactions. The surface excess charge layer in droplets has often been associated with distinct chemistry. Using molecular simulations for droplets with Na+ and Cl- ions we have found that this layer is ≈ 1.5−1.7 nm thick and depending on the droplet size it includes 33%-55% of the total number of ions. Here, we examine the effect of droplet size and nature of ions in the structure of the surface excess charge layer by using molecular dynamics. We find that in the presence of simple ions the thickness of the surface excess charge layer is invariant not only with respect to droplet size but also with respect to the nature of the simple ions and it is not sensitive to fine details of different force fields used in our simulations.</div><div> In the presence of macroions the excess surface charge layer may extend to 2.0. nm. For the same droplet size, iodide and model hydronium ions show considerably higher concentration than the sodium and chloride ions. <br></div><div>We also find that differences in the average water dipole orientation in the presence of cations and anions in this layer are reflected in the charge distributions. Within the surface charge layer, the number of hydrogen bonds reduces gradually relative to the droplet interior where the number of hydrogen bonds is on the average 2.9 for droplets of diameter < 4 nm and 3.5 for larger droplets. The decrease in the number of hydrogen bonds from the interior to the surface is less pronounced in larger droplets. In droplets with diameter < 4 nm and high concentration of ions the charge of the ions is not compensated only by the solvent polarization charge but by the total charge that also includes the other free charge. This finding shows exceptions to the commonly made assumption that the solvent compensates the charge of the ions in solvents with very high dielectric constant. The study provides molecular insight into the bi-layer droplet structure assumed in the equilibrium partitioning model of C. Enke and assesses critical assumptions of the Iribarne-Thomson model for the ion-evaporation mechanism. <br></div>

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