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A computational investigation of the red and blue shifts in hydrogen bonded systems

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Abstract

The present work reports results of computational investigations of hydrogen bonding, with regard to the most common red shift in the vibrational frequency, as well as the less common blue shift in several hydrogen bonded systems. A few new correlations of the frequency shifts with the calculated electrostatic parameters are proposed, thereby generating new insight into both types of the frequency shifts. Thus, the frequency shifts in X—H—-Y hydrogen bonded systems at different H—Y distances are shown to correlate well with the Mulliken charges on H and Y, with the positive and negative charges on Y correlating with the blue and red shift of the frequency of X—H vibration, respectively. The role played by charge transfers at other parts of the interacting system is also discussed.

GRAPHICAL ABSTRACT

Synopsis The blue and red shifts in vibrational frequency in X—H...Y hydrogen bonded systems as a function of H—-Y distance are shown to correlate well with the atomic charges on H and Y as well as other electrostatic parameters.

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References

  1. Jeffrey G A 1997 In An Introduction to Hydrogen Bonding (New York: Oxford University Press)

    Google Scholar 

  2. Arunan E, Desiraju G R, Klein R A, Sadlej J, Scheiner S, Alkorta I, Clary D C, Crabtree R H, Dannenberg J J, Hobza P, Kjaergaard H G, Legon A C, Mennucci B and Nesbitt D J 2011 Definition of the Hydrogen Bond Pure Appl. Chem. 83 1637

    CAS  Google Scholar 

  3. (a) Desiraju G R 2011 A bond by any other name Angew. Chem. Int. Ed. 50 52; (b) Desiraju G R 1991 The C-H...O Hydrogen Bond in Crystals: What is it? Acc. Chem. Res. 24 290

  4. Hobza P and Havlas Z 2000 Blue-Shifting Hydrogen Bonds Chem. Rev. 100 4253

    Article  CAS  Google Scholar 

  5. Joseph J and Jemmis E D 2007 Red-, Blue-, or No-Shift in Hydrogen Bonds: A Unified Explanation J. Am. Chem. Soc. 129 4620

    Article  CAS  Google Scholar 

  6. Li X, Liu L and Schlegel H B 2002 On the physical origin of blue-shifted hydrogen bonds J. Am. Chem. Soc. 124 9639

    Article  CAS  Google Scholar 

  7. Alabugin I V, Monoharan M, Peabody S and Weinhold F 2003 Electronic basis of improper hydrogen bonding: a subtle balance of hyperconjugation and rehybridization J. Am. Chem. Soc. 125 5973

    Article  CAS  Google Scholar 

  8. Li A Y 2007 Chemical origin of blue- and redshifted hydrogen bonds: intramolecular hyperconjugation and its coupling with intermolecular hyperconjugation J. Chem. Phys. 126 154102

    Article  Google Scholar 

  9. (a) Hobza P 2001 The H-index unambiguously discriminates between hydrogen bonding and improper blue-shifting hydrogen bonding Chem. Phys. Phys. Chem. 3 2555; (b) Hobza P and Havlas Z 2002 Improper, blue-shifting hydrogen bond Theor. Chem. Acc. 108 325

  10. Hobza P, Špirko V, Havlas Z, Buchhold K, Reimann B, Barth H and Brutschy B 1999 Anti-hydrogen bond between chloroform and fluorobenzene Chem. Phys. Lett. 299 180

    CAS  Google Scholar 

  11. Rozenberg M, Loewenschuss A and Marcus Y 2000 An empirical correlation between stretching vibration redshift and hydrogen bond length Phys. Chem. Chem. Phys. 2 2699

    Article  CAS  Google Scholar 

  12. Scheiner S and Kar T 2002 Red- versus Blue-Shifting Hydrogen Bonds: Are There Fundamental Distinctions J. Phys. Chem. A 106 1784

    Article  CAS  Google Scholar 

  13. Gilli G and Gilli P 2000 Towards an unified hydrogen-bond theory J. Mol. Struct. 552 1

    Article  CAS  Google Scholar 

  14. Hermansson K 2002 Blue-Shifting Hydrogen Bonds J. Phys. Chem. A 106 4695

    Article  CAS  Google Scholar 

  15. Wang J, Feng Y, Liu L, Li X and Guo Q 2004 On the correlation between the blue shift of hydrogen bonding and the proton donor-proton acceptor distance Chin. J. Chem. 22 642

    CAS  Google Scholar 

  16. Lu P, Liu G and Li J 2005 Existing problems in theoretical determination of red-shifted or blue-shifted hydrogen bond J. Mol. Struct. 723 95

    Article  CAS  Google Scholar 

  17. Wang S, Sahu P K and Lee S 2005 Intermolecular orbital repulsion effect on the blue-shifted hydrogen bond Chem. Phys. Lett. 406 143

    CAS  Google Scholar 

  18. Hoja J, Sax, A F and Szalewicz K 2014 Is Electrostatics Sufficient to Describe Hydrogen-Bonding Interactions? Chem. Eur. J. 20 2292

    Article  CAS  Google Scholar 

  19. Senthilkumar L, Ghanty T K, Ghosh S K and Kolandaivel P 2006 Hydrogen bonding in substituted formic acid dimers J. Phys. Chem. 110 12623

    Article  CAS  Google Scholar 

  20. Senthilkumar L, Ghanty T K and Ghosh S K 2006 Electron density and energy decomposition analysis in hydrogen-bonded complexes of azabenzenes with water, acetamide, and thioacetamide J. Phys. Chem. A 109 7575

    Article  Google Scholar 

  21. Kolandaivel P and Nirmala V 2004 Study of proper and improper hydrogen bonding using Bader’s atoms in molecules (AIM) theory and NBO analysis J. Mol. Struct. 694 33

    Article  CAS  Google Scholar 

  22. Parthasarathy R, Subramanian V and Sathyamurthy N 2006 Hydrogen bonding without borders: An atom in molecules perspective J. Phys. Chem. Lett. 110 3349

    Google Scholar 

  23. Dey A, Mondal S I, Sen S, Ghosh D and Patwari G N 2014 Electrostatics determine vibrational frequency shifts in hydrogen bonded complexes Phys. Chem. Chem. Phys. 16 25247

    Article  CAS  Google Scholar 

  24. Dey A, Mondal S I, Sen S and Patwari G N 2016 Spectroscopic and Ab Initio Investigation of \(\text{ C }-\text{ H }\cdots \text{ N }\) Hydrogen-Bonded Complexes of Fluorophenylacetylenes: Frequency Shifts and Correlations ChemPhysChem 17 2509

    Article  CAS  Google Scholar 

  25. Shirhatti P R, Maity D K and Wategaonkar S 2013 \(\text{ C }-\text{ H }\cdots \text{ Y }\) hydrogen bonds in the complexes of p-cresol and p-cyanophenol with fluoroform and chloroform J. Phys. Chem. A 117 2307

    Article  CAS  Google Scholar 

  26. Banerjee P, Mukhopadhyay D P and Chakraborty T 2015 On the origin of donor O-H bond weakening in phenol-water complexes J. Chem. Phys. 143 204306

    Article  Google Scholar 

  27. Goswami M and Arunan E 2009 The hydrogen bond: a molecular beam microwave spectroscopist’s view with a universal appeal Phys. Chem. Chem. Phys. 11 8974

    Article  CAS  Google Scholar 

  28. Saggu M, Levinson N M and Boxer S G 2012 Experimental Quantification of Electrostatics in \(\text{ X }\text{-- }\text{ H }\cdot \cdot \cdot \pi \) Hydrogen Bonds J. Am. Chem. Soc. 134 18986

  29. Schmidt M W, Baldridge K K, Botaz J A, Elbert S T, Gordon M S, Jensen J, Koseki S, Matsunaga N, Nguyen K A, Su S, Windus T L, Dupuis M and Montgomery J A 1993 General atomic and molecular electronic structure system J. Comp. Chem. 14 1347

    Article  CAS  Google Scholar 

  30. Gilli P, Bertolasi V, Ferretti V and Gilli G 1994 Covalent Nature of the Strong Homonuclear Hydrogen Bond. Study of the O—H...O System by Crystal Structure Correlation Methods J. Am. Chem. Soc. 116 909

    Article  CAS  Google Scholar 

  31. Umeyama H and Morokuma K 1977 The Origin of Hydrogen Bonding. An Energy Decomposition Study J. Am. Chem. Soc. 99 1316

    Article  CAS  Google Scholar 

  32. Saha R, Pan S, Frenking G, Chattaraj P K and Merino G 2017 The strongest CO binding and the highest C–O stretching frequency Phys. Chem. Chem. Phys. 19 2286

    Article  CAS  Google Scholar 

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Acknowledgements

We are thankful to all the three National Science Academies of India for the award of Academy Summer Research Fellowship (2016) and DST, India for the award of INSPIRE fellowship to one of us (MD). SKG thanks DAE, India for the Raja Ramanna Fellowship and UM-DAE-Centre of Excellence for Basic Sciences, Mumbai for a Distinguished Professorship.

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Authors and Affiliations

  1. School of Chemical Sciences, National Institute of Science Education and Research, Bhubaneswar, Khordha, Odisha, 752 050, India

    Mitradip Das

  2. Chemistry Group, Bhabha Atomic Research Centre, Mumbai, Maharashtra, 400 085, India

    Swapan K Ghosh

  3. UM-DAE-Centre for Excellence in Basic Sciences, Vidyanagari Campus, Kalina, Santacruz (East), Mumbai, Maharashtra, 400 098, India

    Swapan K Ghosh

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  1. Mitradip Das
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  2. Swapan K Ghosh
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Correspondence to Swapan K Ghosh.

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Dedicated to the memory of the late Professor Charusita Chakravarty.

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Das, M., Ghosh, S.K. A computational investigation of the red and blue shifts in hydrogen bonded systems. J Chem Sci 129, 975–981 (2017). https://doi.org/10.1007/s12039-017-1304-4

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