Cooperative effects in one-dimensional chains of three-center hydrogen bonding interactions

Parra, Rubén D.; Bulusu, Satya S.; Zeng, Xiao Cheng

doi:10.1063/1.1535441

Cited by 72 publications

(35 citation statements)

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“…The asymptotic percent increase for ͗D o ͘ is close to 80%, which is larger than the extrapolated percent increase in the one-dimensional chains of three-center H bonds of diformamide molecules ͑62%͒, 47 and urea molecules ͑55%͒. 43 The ordering of cooperative enhancement in the calculated asymptotic ͗D o ͘ for carbonic acid ͑20.70 kcal/ mol͒, diformamide ͑14.18͒, 47 and urea ͑10.70͒ 43 supports the view that the degree of cooperativity is proportional to the strength of the H bond. 35 The same conclusion is drawn if a graph of the percent increase of ͗D e ͘ vs n is used instead.…”

Section: Model Systemsmentioning

confidence: 99%

“…Earlier reports 35,47,71,72 have shown the importance of the role of charge transfer interactions involved in the H-bond formations. Molecular units acting simultaneously as both H-bond donor and H-bond acceptor form extended chains or rings in which individual hydrogen bond enhances the strength of each other by mutual polarization.…”

Section: Nbo Analysismentioning

confidence: 99%

“…A similar result was noted in our previous work on linear chains of diformamide molecules, wherein both the 6-31+ G͑d͒ and 6-311+ +G͑2d ,2p͒ basis sets ͑at the MP2 level͒ show an identical rise in H-bond energy upon going from diformamide dimer to pentamer. 47 For computational convenience and given its relatively good performance, the interaction energies for the larger clusters were computed at the MP2 / 6-31+ G͑d͒ level. Table II reports the MP2 / 6-31+ G͑d͒ BSSE-corrected dissociation energies before, D e , and after, D o , zero-point vibrational energy correction.…”

Section: Model Systemsmentioning

confidence: 99%

“…Recently, we reported strong cooperative effects in one-dimensional chains of three centered hydrogen bonding interactions of the former type, using onedimensional chains of the trans-trans conformer of the diformamide molecule. 47 Cooperative effects in onedimensional aggregates of three-centered H bonding of the H 1 AH 2 type have been studied on chains and ribbons of urea and thiourea using various ab initio and semiempirical methods. 43 In this work, we investigate the degree of cooperativity in two-dimensional ring-like structures containing three-centered H bonding with one acceptor and two donors ͑H 1 AH 2 ͒.…”

Section: Introductionmentioning

confidence: 99%

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Cooperative effects in two-dimensional ring-like networks of three-center hydrogen bonding interactions

Parra

Bulusu

Zeng

2005

The Journal of Chemical Physics

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Cooperative effects in two-dimensional cyclic networks containing intermolecular three-centered hydrogen bonding interactions of the type H 1 …A…H 2 are investigated by means of ab intio molecular orbital and density functional theory calculations. Ring-like clusters consisting of three and up to nine monomers of the cis-cis isomer of carbonic acid H 2 CO 3 are used as basic models, where each unit acts simultaneously as a double hydrogen-bond donor and double hydrogen-bond acceptor. Cooperative effects based on binding energies are evident for ͑H 2 CO 3 ͒ n , where n goes from 2 to 9. Thus, the ZPVE-corrected dissociation energy per bifurcated hydrogen bond increases from 11.52 kcal/ mol in the dimer to 20.42 kcal/ mol in the nonamer, i.e., a 77% cooperative enhancement. Cooperative effects are also manifested in such indicators as geometries, and vibrational frequencies and intensities. The natural bond orbital analysis method is used to rationalize the results in terms of the substantial charge delocalization taking place in the cyclic clusters. Cooperativity seems close to reaching an asymptotic limit in the largest ring considered, n = 9.

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Section: Model Systemsmentioning

confidence: 99%

Section: Nbo Analysismentioning

confidence: 99%

Section: Model Systemsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Cooperative effects in two-dimensional ring-like networks of three-center hydrogen bonding interactions

Parra

Bulusu

Zeng

2005

The Journal of Chemical Physics

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“…Como esperado, a energia proveniente do potencial de troca de spins (E Ex (12) ) é sempre positiva, por se tratar de um termo repulsivo derivado do princípio da exclusão de Pauli. Embora o sistema (f) apresente uma contribuição ínfima de -1,71 kcal/mol para a energia eletrostática E (12) C,Resp , comparativamente os valores de -1,51 e -1,26 kcal/mol relacionados aos termos das energias de dispersão E D (20) 129 Canuto et al, 130 Frontera et al, 131 Parra et al 132 e em recente comunicação de Bauer e Spange.…”

Section: Métodos Teóricos De Decomposição De Energiaunclassified

SAPT: ligação de hidrogênio ou interação de van der Waals?

Oliveira¹,

Araújo²

2012

Quím. Nova

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Recebido em 24/11/11; aceito em 27/6/12; publicado na web em 17/9/12 SAPT: HYDROGEN BOND OR van der WAALS INTERACTION? It is through the application of an electronic partition approach called Symmetry-Adapted Perturbation Theory (SAPT) that the nature of hydrogen bonds and van der Waals interactions can be unveiled according to the contribution of electrostatic, charge transfer, exchange repulsion, polarization, and dispersion terms. Among these, electrostatic partition governs the formation of the hydrogen bonds, whose energies are arguably high. However, the weakness of the interaction strength is caused by dispersion forces, whose contribution decisively lead to the stabilization of complexes formed via van der Waals interactions. Keywords: hydrogen bonds; van der Waals interactions; SAPT. INTRODUÇÃOFisicamente, as interações fortes, fracas, eletromagnéticas e gravitacionais governam o contato entre as partículas.1 Destas, é bem estabelecido pela cromodinâmica quântica que as interações fortes ocorrem entre prótons e nêutrons através da ação dos quarks e glúons, 2 cujo resultado é a formação do núcleo atômico denso e compacto. Presente em nível nuclear, as interações fracas são 10 13 menos intensas e são caracterizadas pelas manifestações dos bósons W (Weak nuclear force) e Z (Zero).3 Interações eletromagnéticas são típicas de partículas elementares carregadas 4 e são 10 2 mais fracas em relação às interações fortes. Por fim, a geometrodinâmica estabelece que as interações gravitacionais são 10 42 mais amenas e estão presentes em sistemas com massas macroscopicamente mensuráveis, 5 como estrelas, galáxias e todo o universo. No cerne da química atômico--molecular, as interações consideradas fracas com características puramente eletrostáticas são as mais importantes, pois os sistemas são interpretados como sendo ligados 6,7 e não covalentes, 8,9 e nestas circunstâncias átomos formam as ligações químicas 10 e moléculas atingem condições eletrônicas propícias para formarem estruturas intermoleculares estáveis. As interações intituladas de van der Waals foram assim concebidas em reconhecimento ao físico neerlândes Johannes Diederik van der Waals pelos seus estudos com substâncias gasosas e líquidas, em uma proposta que objetivava a otimização dos modelos de Boyle e Charles 54 através da descrição do tamanho molecular e a força intermolecular atuante, a qual é composta pelas contribuições de Keesom (interação entre dipolo permanente--dipolo permanente), 55 Debye (interação entre dipolo permanente--dipolo induzido) 56 e London (interação entre dipolo induzido-dipolo induzido). 57 As interações de van der Waals têm sido foco de muitos pesquisas, principalmente no aprimoramento de alguns métodos que falham na captura dos efeitos provenientes das forças de dispersão. 58As ligações de hidrogênio ou interações de van der Waals são, de fato, alicerces de suma importância para a Biologia, Medicina, Química, Engenharia, Física 59 e áreas correlatas. Entretanto, dentro da comunidade científica ainda persiste um intenso deba...

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Strong Short‐Range Cooperativity in Hydrogen‐Bond Chains

et al. 2017

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Chains of hydrogen bonds such as those found in water and proteins are often presumed to be more stable than the sum of the individual Hbonds.However,the energetics of cooperativity are complicated by solvent effects and the dynamics of intermolecular interactions,m eaning that information on cooperativity typically is derived from theory or indirect structural data. Herein, we present direct measurements of energetic cooperativity in an experimental system in which the geometry and the number of Hbonds in achain were systematically controlled. Strikingly,w ef ound that adding asecond H-bond donor to form achain can almost double the strength of the terminal Hbond, while further extensions have little effect. The experimental observations add weight to computations whichh ave suggested that strong, but shortrange cooperative effects mayo ccur in H-bond chains.Chainsofhydrogenbondsareprevalentstructural motifs in supramolecular and biological systems. Hbonds are widely proposed to exhibit positive cooperativity, [1] which may be manifested by acombination of conformational [1,2] and electronic effects that may make ac hain more stable than the sum of its parts.[3] Such cooperative effects have been shown to influence reactivity, [4] to contribute to the structure,i nteractions,a nd properties of biomolecules and materials, [5] and to facilitate the communication of chemical information.[6] Hbonded water clusters and chains have been isolated in the solid state [7] and studied experimentally in both liquid and gas phases.[8] Although many nanoscale and bulk properties may be influenced by the cooperativity of H-bond networks,itisnot possible to directly quantify interaction energies from structural or vibrational characteristics.I na ddition, discussion of the relative contributions of electrostatics,p olarization, and covalencyi nHbond cooperativity [5b, 9] is further exacerbated by the challenge of considering the influence of the surrounding solvent.Herein, we have employed synthetic molecular balances [10] to directly measure the effect of H-bond-chain length on the strength of H-bonding interactions in solution. At the outset of our investigation we identified the series of phenol, catechol, and pyrogallol ( Figure 1B)a sapertinent model system for examining cooperativity in H-bond chains.Indeed, H-bond chains have previously been proposed to contribute to the supramolecular properties of catechol and pyrogallol derivatives. [3b, 11] We reasoned that the pre-organization and proximity of the intramolecular H-bond donors and acceptors in this series of compounds would minimize conformational entropic effects to allow examination of cooperative electronic influences.I nitially we measured the experimental complexation Gibbs energies of phenol, catechol, and pyrogallol with the strong H-bond acceptor tri-n-butylphosphine oxide using 31 PNMR spectroscopy.T he binding energies became more favorable as the number of OH groups was increased ( Figure 1A). Such atrend could be rationalized by cooperative e...

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Cooperative effects in one-dimensional chains of three-center hydrogen bonding interactions

Cited by 72 publications

References 36 publications

Cooperative effects in two-dimensional ring-like networks of three-center hydrogen bonding interactions

Cooperative effects in two-dimensional ring-like networks of three-center hydrogen bonding interactions

SAPT: ligação de hidrogênio ou interação de van der Waals?

Strong Short‐Range Cooperativity in Hydrogen‐Bond Chains

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