Soliton Modelling for the Proton Transfer in Hydrogen-Bonded Systems

Pnevmatikos, St.; Savin, A. V.; Zolotaryuk, A. V.

doi:10.1007/978-1-4615-3444-0_6

Cited by 3 publications

(2 citation statements)

References 38 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Proton transfer reactions have attracted widespread attention in recent years, particularly in relation to understanding fundamental reactions in varied research areas; from electrochemical to biological and atmospheric systems [1–6]. Femtosecond IR spectroscopy has been used to track the transfer of an acidic hydroxyl (OH) proton from a photolabile acid to acetic acid and its derivatives [7, 8], and even to human serum albumin [9–11].…”

Section: Introductionmentioning

confidence: 99%

A quantum chemical investigation of energetic, geometric, mechanistic, and kinetic aspects of multiple proton transfer in cyclic H₂O, H₂S, and H₂O‐H₂S clusters

Monu,

Oram,

Bandyopadhyay

2024

Int J of Quantum Chemistry

View full text Add to dashboard Cite

Multiple proton transfers in cyclic homogenous and mixed H2O‐H2S clusters from trimers to pentamers have been investigated at an affordable and accurate level of theory. Reaction force and Wiberg bond index analyses showed the process to be nearly synchronous in all the homogenous clusters, while asynchronous in the mixed clusters; always initiated by movement of the SH protons to the H‐bonded O atoms. The barriers for proton transfers exhibited a complex pattern, decreasing initially from the homogeneous H2O cluster upon replacement of one H2O by an H2S moiety and subsequently rising monotonically with each subsequent replacement(s) to becoming highest in pure H2S clusters. Finally, the impact of the energetic and mechanistic modulations on the proton transfer kinetics has been studied.

show abstract

Section: Introductionmentioning

confidence: 99%

A quantum chemical investigation of energetic, geometric, mechanistic, and kinetic aspects of multiple proton transfer in cyclic H₂O, H₂S, and H₂O‐H₂S clusters

Monu,

Oram,

Bandyopadhyay

2024

Int J of Quantum Chemistry

View full text Add to dashboard Cite

show abstract

“…It should be noted that a sequence of noncovalent interactions does not necessarily lead to strengthening as cases of weakening of the individual interactions have been documented and studied [26][27][28]. Another important characteristic of the hydrogen bond that has been thoroughly investigated is its potential to facilitate the transfer of a proton from one molecular unit to another [29][30][31][32][33]. Given its similarity with a hydrogen bond [34], a halogen bond may in turn be thought of as one step in the process of transferring a halonium ion from one unit to another.…”

Section: Introductionmentioning

confidence: 99%

Cooperativity and halonium transfer in the ternary NCI···CH 3 I··· - CN halogen-bonded complex: An ab initio gas phase study

Parra

2024

Preprint

View full text Add to dashboard Cite

Context The strength and nature of the two halogen bonds in the NCI···CH3I···−CN halogen-bonded ternary complex are studied in the gas phase via ab initio calculations. Different indicators of halogen bond strength were employed to examine the interactions including geometries, complexation energies, NBO Wiberg bond indices, and AIM parameters. The results show that the halogen bond is strong and partly covalent in nature when CH3I donates the halogen bond, but weak and noncovalent in nature when CH3I accepts the halogen bond. Significant halogen bond cooperativity emerges in the ternary complex relative to the corresponding heterodimer complexes, NCI···CH3I and CH3I···−CN, respectively. For example, the CCSD(T) complexation energy of the ternary complex (-18.27 kcal/mol) is about twice the sum of the complexation energies of the component dimers (-9.54 kcal/mol). The halonium transfer reaction that converts the ternary complex into an equivalent one was also investigated. The electronic barrier for the halonium transfer was calculated to be 6.70 kcal/mol at the CCSD(T) level. Although the MP2 level underestimates and the MP3 overestimates the barrier, their calculated MP2.5 average barrier (6.44 kcal/mol) is close to that of the more robust CCSD(T) level. Insights on the halonium ion transfer reaction was obtained by examining the reaction energy and force profiles along the intrinsic reaction coordinate, IRC. The corresponding evolution of other properties such as bond lengths, Wiberg bond indices, and Mulliken charges provides specific insight on the extent of structural rearrangements and electronic redistribution throughout the entire IRC space.Methods The MP2 method was used for geometry optimizations. Energy calculations were performed using the CCSD(T) method. The aug-cc-pVTZ basis set was employed for all atoms other than iodine for which the aug-cc-pVTZ-PP basis set was used instead.

show abstract

Impurity effects in a double sine-Gordon equation

Pavlopoulos

Bountis

1994

Physics Letters A

View full text Add to dashboard Cite

Soliton Modelling for the Proton Transfer in Hydrogen-Bonded Systems

Cited by 3 publications

References 38 publications

A quantum chemical investigation of energetic, geometric, mechanistic, and kinetic aspects of multiple proton transfer in cyclic H₂O, H₂S, and H₂O‐H₂S clusters

A quantum chemical investigation of energetic, geometric, mechanistic, and kinetic aspects of multiple proton transfer in cyclic H₂O, H₂S, and H₂O‐H₂S clusters

Cooperativity and halonium transfer in the ternary NCI···CH 3 I··· - CN halogen-bonded complex: An ab initio gas phase study

Impurity effects in a double sine-Gordon equation

Contact Info

Product

Resources

About

Soliton Modelling for the Proton Transfer in Hydrogen-Bonded Systems

Cited by 3 publications

References 38 publications

A quantum chemical investigation of energetic, geometric, mechanistic, and kinetic aspects of multiple proton transfer in cyclic H2O, H2S, and H2O‐H2S clusters

A quantum chemical investigation of energetic, geometric, mechanistic, and kinetic aspects of multiple proton transfer in cyclic H2O, H2S, and H2O‐H2S clusters

Cooperativity and halonium transfer in the ternary NCI···CH 3 I··· - CN halogen-bonded complex: An ab initio gas phase study

Impurity effects in a double sine-Gordon equation

Contact Info

Product

Resources

About

A quantum chemical investigation of energetic, geometric, mechanistic, and kinetic aspects of multiple proton transfer in cyclic H₂O, H₂S, and H₂O‐H₂S clusters

A quantum chemical investigation of energetic, geometric, mechanistic, and kinetic aspects of multiple proton transfer in cyclic H₂O, H₂S, and H₂O‐H₂S clusters