Ab initio NMR study of the isomeric hydrogen‐bonded methanol–water complexes

Fileti, Eudes Eterno; Canuto, Sylvio

doi:10.1002/qua.20437

Cited by 18 publications

(13 citation statements)

References 60 publications

(51 reference statements)

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“…In contrast, although BH b bond length decreases, red shift (by 2.0–4.5cm −1 ) in symmetric BH b stretching is observed for Me 3 P···DB, MeOH···DB, Me 2 O···DB, and Me 2 S···DB complexes. The observed shift (blue or red) in H b stretching frequencies are in line with the reported interactions involving H b …”

Section: Vibrational Frequency Shiftsupporting

confidence: 89%

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B−H_b←:X (X= N, O, P, S, F, Cl, Br) interactions: A density functional study

Saha

Bhattacharyya

2018

Int J of Quantum Chemistry

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Density functional theory calculation on BAH b :X interaction (X5 N, O, P, S, F, Cl, Br) is performed. HOMO energy predicts the feasibility of such complexation. Steric and electronic effects play significant role on geometry of the complexes. Interaction energy suggests that the interaction is moderately strong (< 5.00 kcal mol 21 ) in nature and the complexes are stable in both gas and solvent phase. Electron donating group on: X facilitates the interaction whereas electron withdrawing group impedes the same. MP2 and CCSD(T) calculations further confirm the suitability of xB97X-D and M06-2X functional for studying such interactions. Dispersive interaction is the primary mode of interaction in stabilizing the complexes. 1 H NMR and IR study are also performed.Thermochemical analysis advocates exothermic nature of complexation.B2H b :X interaction, CCSD(T), DFT, MP2, stabilization energy, thermochemical analysis 1 | I N TR ODU C TI ON Noncovalent interactions such as hydrogen bonding, stacking, dispersion interaction, hydrophobic interaction, interaction with p systems (anionÁÁÁp, CAHÁÁÁp, OAHÁÁÁp, NAHÁÁÁp, SAHÁÁÁp, cationÁÁÁp) and halogen bonding have drawn attention owing to their potential application in different fields [1][2][3][4] and play significant role in controlling different physical, chemical, and biological phenomena in crystal engineering, drug designing, protein folding, molecular recognition process, and supramolecular chemistry. [2,[5][6][7][8][9][10][11][12][13][14] These interactions are classified depending on their origin, nature, and strength. [8] Hydrogen bonding is one of the most versatile and extensively studied noncovalent interaction [15][16][17] that plays an essential role in the function, dynamics, and structure of biological and chemical systems. Hydrogen bonding interactions can be either conventional or nonconventional. [18] In conventional hydrogen bonding, DAHÁÁÁA, both D (donor) and A (acceptor) atoms are highly electronegative (usually N, O, F) whereas in nonconventional case D and A may both be less electronegative.A relatively new and less known nonconventional interaction is the BAHÁÁÁp interaction in which both terminal (H t ) and bridging (H b ) hydrogens of boranes interact with interaction in which both terminal (H t ) and bridging (H b ) hydrogens of boranes interact with electron rich p systems. [19,20] However, partially negative H t (H d-) of borane is reluctant to form stable BAH t ÁÁÁp interactions. In contrast, H b is partially positive (H d1 ) due to its involvement in the formation of two electron-three center (2eA3c) bond and thereby results a stable BAH b ÁÁÁp interaction. [20] Recently, new type of noncovalent interaction involving lone pairs (nonbonded pairs) has also been explored. [8] Lone pair of electrons not only control the geometry but also play a decisive role in the chemistry of the species. Amongst the interactions involving lone pair, lone pairÁÁÁp interaction is widely studied [4,18] and was first identified in the structure of Z-DNA. [21] How...

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Section: Vibrational Frequency Shiftsupporting

confidence: 89%

“…Recent literature also reported both red (∼ 8 cm −1 ) and blue (∼ 6 cm −1 ) shift in symmetric BH b stretching in the complexes involving BH b ···π interaction . We also reported similar shift in symmetric H b stretching in the complexes formed between un‐doped/doped coronene and tetraborane (10) .…”

Section: Vibrational Frequency Shiftsupporting

confidence: 81%

B−H_b←:X (X= N, O, P, S, F, Cl, Br) interactions: A density functional study

Saha

Bhattacharyya

2018

Int J of Quantum Chemistry

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“…Com funções de base pequenas, a descrição do ambiente molecular não é suficiente e pode levar a erros. Por isso, o cálculo da suscetibilidade magnética deve ser realizado com funções de base extensas [37][38][39] , contendo funções difusas e de polarização, de maneira a obter dados confiáveis.…”

Section: Mecânica Quânticaunclassified

Elucidação estrutural de substâncias orgânicas com auxílio de computador: evoluções recentes

Stefani¹,

Nascimento²,

Costa³

2007

Quím. Nova

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“…Um esforço considerávelé associadoà compreensão destes agregados isolados onde as moléculas estão interagindo através de ligações de hidrogênio [150,151,170,198,199,[204][205][206][207] Na estrutura 1:1B queé a estrutura onde a molécula deágua está localizada acima do plano do anel aromático, osátomos de hidrogênio daágua apontam para os sítios dos nitrogênios da molécula de pirazina, e não para a nuvem π do anel como acontece com a ligação de hidrogênio presente no sistema benzeno-água [174]. O fato dos hidrogênios apontarem para os nitrogênios impede o movimento livre de rotação da molécula deágua sobre o anel, como acontece no caso benzeno-água [174,204,214,215].…”

Section: Ligação De Hidrogênio Pirazina-águaunclassified

Estabilidade isomérica e ligações de hidrogênio em agregados e líquidos moleculares

Fileti¹

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AgradecimentosMuitas pessoas foram fundamentais durante os quatro anos de doutorado que resultaram nesta tese. Todas elas foram importantes, mas algumas foram imprescindíveis. Na classe das importantes estão os amigos que fiz durante todo este período no departamento, os quais sempre me suportaram (nos dois sentidos!!!) e me alavancaram para cima. Vocês meus amigos, têm uma boa parcela de "culpa"para a conclusão desta tese. Agradeço aos colegas de sala, pelaótima convivência, o que certamente influenciou neste trabalho. Na classe dos imprescindíveis estão meu orientador, a quem eu sempre chamei e vou continuar chamando por muito tempo de meu "pai científico", professor Sylvio Canuto, que soube durante todos estes sete anos de convivência (adaptação matemática → física, mestrado e doutorado) conduzir-me na ciência com muita paciência, dedicação e amizade. Sou muito grata, por ter feito parte de seu seleto grupo de alunos, e com isso ter tido a chance de aprender com ele não só sobre a física, mas sobreética na vida científica e sobre a vida de um modo geral. Também na classe dos imprescindíveis está a professora Kaline, que sempre influenciou os trabalhos de todos do grupo de forma construtiva e enriquecedora, a quem também sou muito grata pela enorme amizade. Espero poder contar com os dois por muitos anosà frente. Ao CNPq pelo suporte financeiro direto eà FAPESP pelas máquinas sem as quais nada disso seria possível. AbstractIn this work, we study the isomeric stability of isolated molecules and molecular clusters. We study the change of some electronic properties of molecular clusters in gas and liquid phases. The first application is the relative isomeric stability of isolated AlP 3 in C 2v , C 3v and C s symmetries. We analyze the conformational structure and the total energy of the three isomers using sophisticated quantum chemistry calculations and using CCSD(T)/cc-pVXZ (X = 2, 3, 4 and 5) level and extrapole to the infinite basis set limit. The locations of the two states on the potential energy hyper-surface are obtained and show that they represent well-defined and stable isomers. We also investigate the HCN· · · HOH and H 2 O· · · HCN clusters in gas phase, using ab initio calculations to obtain the optimized structure of these two molecular clusters. We present a systematic study of the stability of the H 2 O· · · HCN and HCN· · · HOH complexes calculating the binding energy of both systems using the aug-cc-pVXZ basis sets with X=2,3,4 and extending the results to the infinite limit. At the best theoretical level, CCSD(T), the H 2 O· · · HCN cluster is more stable than HCN· · · HOH by ∼ 1.5 kcal/mol. In the second part of our work, we investigate the electronic modifications in molecular clusters due to the different environments of these clusters, the gas and the liquid phases. We analyze the pyrazine-water clusters (1:1 and 1:2) obtained in gas and liquid phases and compare the structure and electronic clusters properties. For the 1:1 pyrazine-water clusters we compare the structures, total energy and...

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Ab initio NMR study of the isomeric hydrogen‐bonded methanol–water complexes

Cited by 18 publications

References 60 publications

B−H_b←:X (X= N, O, P, S, F, Cl, Br) interactions: A density functional study

B−H_b←:X (X= N, O, P, S, F, Cl, Br) interactions: A density functional study

Elucidação estrutural de substâncias orgânicas com auxílio de computador: evoluções recentes

Estabilidade isomérica e ligações de hidrogênio em agregados e líquidos moleculares

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Ab initio NMR study of the isomeric hydrogen‐bonded methanol–water complexes

Cited by 18 publications

References 60 publications

B−Hb←:X (X= N, O, P, S, F, Cl, Br) interactions: A density functional study

B−Hb←:X (X= N, O, P, S, F, Cl, Br) interactions: A density functional study

Elucidação estrutural de substâncias orgânicas com auxílio de computador: evoluções recentes

Estabilidade isomérica e ligações de hidrogênio em agregados e líquidos moleculares

Contact Info

Product

Resources

About

B−H_b←:X (X= N, O, P, S, F, Cl, Br) interactions: A density functional study

B−H_b←:X (X= N, O, P, S, F, Cl, Br) interactions: A density functional study