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X-H⋯C hydrogen bonds in n-alkane-HX (X = F, OH) complexes are stronger than C-H⋯X hydrogen bonds

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Abstract

Computational study of X-H⋯C and C-H⋯X hydrogen bonds in n-alkane-HX complexes (X =F,OH, alkane =propane, butane, pentane) has been carried out in this work. Ab initio and density functional theories were used for this study. For n-alkane-H2O complexes both O⋯H-C and O–H⋯C hydrogen bonded complex have been found, while for n-alkane-HF complexes, our attempt to optimize F⋯H-C H-bond was not successful. Like most of the hydrogen bonded systems, strong correlation between binding energy and stretching frequency of H-F and O-H stretching mode was observed. The values of electron density and Laplacian of electron density are within the accepted range for hydrogen bonds. In all these cases, X-H⋯C hydrogen bonds are found to be stronger than C-H⋯X hydrogen bonds.

O–H⋯C hydrogen bond in n-butane represents n-alkane-HX (X = F, OH) complexes. X-H⋯C hydrogen bonds are found to be stronger than C-H⋯X hydrogen bonds.

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Acknowledgements

RP thanks Academy of Science for Developing World for TWAS-UNESCO Associateship, Prof. Rangarajan, the then Chairman, International Relation Cell, Indian Institute of Science and all the lab-members of Prof. Arunan’s laboratory. We thank the Supercomputer Education Research Centre at the Indian Institute of Science for computational facilities. RP would like to acknowledge Prof E Krishnakumar and Tata Institute of Fundamental Research (TIFR), Mumbai, India, for the visiting scientist position in January 2013 and January 2015 where the final form of this manuscript was prepared and revised. RP also acknowledges Centre for Science and Technology of the Non-Aligned and Other Developing Countries (NAM S&T Centre), New Delhi, for providing travel grants to visit TIFR in January 2015 and Dr. Leela Pradhan Joshi, Department of Physics, Amrit Campus, Tribhuvan University.

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Authors and Affiliations

  1. Department of Physics, Amrit Campus, Tribhuvan University, Kathmandu, Nepal

    R PARAJULI

  2. Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bengaluru, 560012, India

    E ARUNAN

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  1. R PARAJULI
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Correspondence to R PARAJULI.

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Supplementary Information

Supplementary information is available at www.ias.ac.in/chemsci. In table S1, coordinate of propane optimized at B3LYP/6-311 ++g** is given. Positions of maximum and minimum values of ESPs and the values of ESPs are given in S2. The corresponding values for butane and pentane are given in tables S3, S4, S5 and S6, respectively. Some relevant parameters optimized with M05-2X/6-311 ++G** level of theory of the complex are presented in tables S7 and S8. Penetration parameters, bonding radius of acceptor, non-bonding radius of hydrogen atom, bonding radius of hydrogen atom are given in table S9. Changes in atomic volumes, populations, and energies are given in tables S10, S11 and S12, respectively. In table S13, changes in atomic first moments of the “H” of F-H⋯alkane complexes are given. The optimized structure of Water⋯alkane complex at B3LYP/6-311 ++g** level of theory is given in figure S1.

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PARAJULI, R., ARUNAN, E. X-H⋯C hydrogen bonds in n-alkane-HX (X = F, OH) complexes are stronger than C-H⋯X hydrogen bonds. J Chem Sci 127, 1035–1045 (2015). https://doi.org/10.1007/s12039-015-0861-7

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