On the Correlation between Bond-Length Change and Vibrational Frequency Shift in Hydrogen-Bonded Complexes:  A Computational Study of Y···HCl Dimers (Y = N2, CO, BF)

2005 ◽  
Vol 127 (44) ◽  
pp. 15515-15520 ◽  
Author(s):  
Sean A. C. McDowell ◽  
A. David Buckingham
Keyword(s):  
Frequency Shift ◽  
Bond Length ◽  
Vibrational Frequency ◽  
Computational Study ◽  
Length Change ◽  
Bonded Complexes ◽  
Hydrogen Bonded

The nature of the bond-length change upon molecule complexation

2010 ◽  
Vol 75 (3) ◽  
pp. 243-256 ◽  
Author(s):  
Weizhou Wang ◽  
Yu Zhang ◽  
Baoming Ji
Keyword(s):  
Charge Transfer ◽  
Complex Formation ◽  
Bond Length ◽  
Electrostatic Interaction ◽  
Length Change ◽  
Attractive Interaction ◽  
Charge Transfer Interaction ◽  
The Difference ◽  
Hydrogen Bonded

The nature of the bond-length change upon molecule complexation has been investigated at the MP2/aug-cc-pVTZ level of theory. Our results have clearly shown that the X–Y bond-length change upon complex formation is determined mainly by the electrostatic attractive interaction and the charge-transfer interaction. In the case of strongly polar bond, the electrostatic interaction always causes bond elongation while in the case of weakly polar bond it causes bond contraction. The charge-transfer interaction generally results in the X–Y bond elongation; either it is a more polar bond or it is a less polar bond. Employing this simple “electrostatic interaction plus charge-transfer interaction” explanation, we explained and predicted many interesting phenomena related to the bond-length change upon molecule complexation. In addition, the difference between the origin of the bond-length change upon hydrogen-bonded complex formation and the origin of the bond-length change upon halogen-bonded complex formation was also discussed.

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