Similar Strength of the NH···O and NH···S Hydrogen Bonds in Binary Complexes

Andersen, Cecilie L.; Jensen, Christine S.; Mackeprang, Kasper; Du, Lin; Jørgensen, Solvejg; Kjaergaard, Henrik G.

doi:10.1021/jp5086679

Cited by 58 publications

(53 citation statements)

References 63 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…They used a range of values that have been previously suggested for  b and  2  b (0.002 <  b < 0.034 au; 0.024 <  2  b < 0.139 au) to identify and characterize O⋯H(-C) hydrogen bonding in molecular complexes [66]; however, as we will show below, these may indeed be a useful guide, but should not be treated as a prerequisite for the identification of hydrogen bonding in chemical systems since non-covalent interactions, in general, do not have strict boundaries [42,43,46,58]. We will also demonstrate that because of its stringent criteria QTAIM sometime fails to identify weakly bound and van der Waals interactions in chemical systems [67][68][69][70][71]; this is the reason we employed the RDG-NCI approach to investigate the details of the bonding topologies involved.…”

Section: Methodsmentioning

confidence: 91%

“…Unequivocally, the bcp is the point where one finds no difference between QTAIM and RDG. elucidated in several recent studies by the Kjaergaard group [67][68][69][70][71], in which it was shown that the experimentally-determined weakly bound and van der Waals interactions in molecular systems can be successfully identified and characterized by RDG-NCI, which may or may not be identified with QTAIM due to its stringent criteria.…”

Section: A Reduced Density Gradient (Rdg) Description Of Non-covalentmentioning

confidence: 99%

See 1 more Smart Citation

Halogen in materials design: Revealing the nature of hydrogen bonding and other non-covalent interactions in the polymorphic transformations of methylammonium lead tribromide perovskite

Varadwaj

Marques

Yamashita

2018

Materials Today Chemistry

View full text Add to dashboard Cite

Methylammonium lead tribromide (CH 3 NH 3 PbBr 3 ) perovskite as a photovoltaic material has attracted a great deal of recent interest. Factors that are important in their application in optoelectronic devices include their fractional contribution of the composition of the materials as well as their microscopic arrangement that is responsible for the formation of well-defined macroscopic structures. CH 3 NH 3 PbBr 3 assumes different polymorphs (orthorhombic, tetragonal and cubic) depending on the evolution temperature of the bulk material. An understanding of the structure of these compounds will assist in rationalizing how halogen-centered non-covalent interactions play an important role in the rational design of these materials. Density functional theory (DFT) calculations have been performed on polymorphs of CH 3 NH 3 PbBr 3 to demonstrate that the H atoms on C of the methyl group in CH 3 NH 3 + entrapped within a PbBr 6 4-perovskite cage are not electronically innocent, as is often contended. We show here that these H atoms are involved in attractive interactions with the surrounding bromides of corner-sharing PbBr 6 4-octahedra of the CH 3 NH 3 PbBr 3 cage to form Br•••H(-C) hydrogen bonding interactions. This is analogous to the way the H atoms on N of the -NH 3 + group in CH 3 NH 3 + form Br•••H(-N) hydrogen bonding interactions to stabilize the structure of CH 3 NH 3 PbBr 3 . Both these hydrogen bonding interactions are shown to persist regardless of the nature of the three polymorphic forms of CH 3 NH 3 PbBr 3 . These, together with the Br•••C(-N) carbon bonding, the Br•••N(-C) pnictogen bonding, and the Br•••Br lump-hole type intermolecular non-covalent interactions identified for the first time in this study, are shown to be collectively responsible for the eventual emergence of the orthorhombic geometry of the CH 3 NH 3 PbBr 3 system. These conclusions are arrived at from a systematic analysis of the results obtained from combined DFT, Quantum Theory of  Corresponding Supporting Information and the ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/xxxxxxx Atoms in Molecules (QTAIM), and Reduced Density Gradient Non-Covalent Interaction (RDG-NCI) calculations carried out on the three temperature-dependent polymorphic geometries of CH 3 NH 3 PbBr 3 .

show abstract

Section: Methodsmentioning

confidence: 91%

Section: A Reduced Density Gradient (Rdg) Description Of Non-covalentmentioning

confidence: 99%

Halogen in materials design: Revealing the nature of hydrogen bonding and other non-covalent interactions in the polymorphic transformations of methylammonium lead tribromide perovskite

Varadwaj

Marques

Yamashita

2018

Materials Today Chemistry

View full text Add to dashboard Cite

show abstract

“…[14][15][16][17][18][19][20][21][22] With this method, equilibrium constants of complex formation are determined from the definition of the equilibrium constant…”

Section: Introductionmentioning

confidence: 99%

The effect of large amplitude motions on the vibrational intensities in hydrogen bonded complexes

Mackeprang

Hänninen

Halonen

et al. 2015

The Journal of Chemical Physics

Self Cite

View full text Add to dashboard Cite

We have developed a model to calculate accurately the intensity of the hydrogen bonded XH-stretching vibrational transition in hydrogen bonded complexes. In the Local Mode Perturbation Theory (LMPT) model, the unperturbed system is described by a local mode (LM) model, which is perturbed by the intermolecular modes of the hydrogen bonded system that couple with the intramolecular vibrations of the donor unit through the potential energy surface. We have applied the model to three complexes containing water as the donor unit and different acceptor units, providing a series of increasing complex binding energy: H2O⋯N2, H2O⋯H2O, and H2O⋯NH3. Results obtained by the LMPT model are presented and compared with calculated results obtained by other vibrational models and with previous results from gas-phase and helium-droplet experiments. We find that the LMPT model reduces the oscillator strengths of the fundamental hydrogen bonded OH-stretching transition relative to the simpler LM model.

show abstract

“…The stability of these complexes are indicated by their equilibrium BE, −7.07 kcal/ mol (Scheme 2a) and −7.60 kcal/mol (Scheme 2b), shown in Table 3, which are consistent with previous studies. 59,60 The BE for SO 2 adsorption at the amine site for the various structures shown in Scheme 1 were compared at the B3LYP/6-31G** and 6-31+G* levels and are reported in Table 3.…”

Section: Introductionmentioning

confidence: 99%

Experimental and Theoretical Investigation of SO₂ Adsorption over the 1,3-Phenylenediamine/SiO₂ System

Miller¹,

Chuang

2015

J. Phys. Chem. C

View full text Add to dashboard Cite

The reversible adsorption of SO 2 on 1,3-phenylenediamine was investigated using the step transient response technique coupled with operando infrared spectroscopy, mass spectrometry, UV−vis spectrometry, and density functional theory (DFT). At 50°C, the reaction of SO 2 at the amine site resulted in fixation of sulfur as hydrogen-bonded SO 3 2− (sulfite) and SO 4 2− (sulfate) species. Simulated infrared and UV−vis spectra at the DFT B3LYP/6-31G(d,p) level were compared to the experimental results to help characterize the infrared spectra, molecular interactions, and bonding of the adsorbing species. The theoretically calculated binding energies revealed the sulfite and sulfate species bind stronger at the ammonium sites as compared to the amine site, which agrees with the infrared spectroscopic observations. Temperature-programmed desorption showed a capacity of 1.39 mol SO 2 /mol sorbent for pure 1,3-phenylenediamine and 2.8 mol SO 2 /mol sorbent for the SiO 2 supported sorbent. The presence of sulfite and sulfate in the sorbent layer at 50°C resulted in the oxidative degradation of the amine site to produce −NO 2 groups and deactivation of adsorption sites in the sorbent. The infrared data indicates that the adsorbed sulfite and sulfate species remained strongly bonded at the ammonium site, whereas the SO 2 , sulfite, and sulfate species at the amine site may be thermally desorbed from the sorbent. The retained SO 3 2− and SO 4 2− species led to the rapid deactivation of the sorbent during multicycle testing. INTRODUCTIONThe separation of sulfur dioxide (SO 2 ) from the flue gas in fossil fuel combustion processes are of particular interest for two primary reasons: (i) SO 2 is harmful to human health and the environment and (ii) SO 2 has the capability of poisoning the active site of various CO 2 capture technologies. 1,2 The mechanism of active site deactivation for amine-based sorbents is generally attributed to the irreversible adsorption of SO 2 and its competitive adsorption with CO 2 . The sorbent's capability to avoid irreversible reactions with SO 2 is an important characteristic for postcombustion applications. A solid amine sorbent for SO 2 removal having high adsorption capacity, longterm regeneration capacity, and low regeneration energy requirement may also improve plant operating costs. Our focus in investigating an amine-based sorbent for SO 2 removal is to study the amine reactive site in order to gain a greater understanding of the SO 2 −amine interactions with the purpose of creating a more effective SO 2 solid sorbent for the large-scale postcombustion scrubbing application.Recently, ionic liquids (ILs) have been proposed as adsorbents for acid gases such as SO 2 , 3−9 CO 2 , 10−14 and H 2 S, 15−17 as compared to technologies developed over the last several decades for flue gas desulfurization (FGD), such as limestone scrubbing, ammonia scrubbing, and adsorption by organic solvents. 18−20 These previous technologies have inherent disadvantages such as the production of large quantities of was...

show abstract

Similar Strength of the NH···O and NH···S Hydrogen Bonds in Binary Complexes

Cited by 58 publications

References 63 publications

Halogen in materials design: Revealing the nature of hydrogen bonding and other non-covalent interactions in the polymorphic transformations of methylammonium lead tribromide perovskite

Halogen in materials design: Revealing the nature of hydrogen bonding and other non-covalent interactions in the polymorphic transformations of methylammonium lead tribromide perovskite

The effect of large amplitude motions on the vibrational intensities in hydrogen bonded complexes

Experimental and Theoretical Investigation of SO₂ Adsorption over the 1,3-Phenylenediamine/SiO₂ System

Contact Info

Product

Resources

About

Similar Strength of the NH···O and NH···S Hydrogen Bonds in Binary Complexes

Cited by 58 publications

References 63 publications

Halogen in materials design: Revealing the nature of hydrogen bonding and other non-covalent interactions in the polymorphic transformations of methylammonium lead tribromide perovskite

Halogen in materials design: Revealing the nature of hydrogen bonding and other non-covalent interactions in the polymorphic transformations of methylammonium lead tribromide perovskite

The effect of large amplitude motions on the vibrational intensities in hydrogen bonded complexes

Experimental and Theoretical Investigation of SO2 Adsorption over the 1,3-Phenylenediamine/SiO2 System

Contact Info

Product

Resources

About

Experimental and Theoretical Investigation of SO₂ Adsorption over the 1,3-Phenylenediamine/SiO₂ System