scholarly journals Correlation between Bond-Length Change and Vibrational Frequency Shift in Hydrogen-Bonded Complexes Revisited

2012 ◽  
Vol 28 (03) ◽  
pp. 499-503 ◽  
Author(s):  
ZHANG Yu ◽  
◽  
MA Ning ◽  
WANG Wei-Zhou
Keyword(s):  
Frequency Shift ◽  
Bond Length ◽  
Vibrational Frequency ◽  
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.

Theoretical study of H bonds of HArF and HF with isoelectronic systems N2, CO, and BF

2010 ◽  
Vol 88 (4) ◽  
pp. 352-361
Author(s):  
An Yong Li ◽  
Li Juan Cao ◽  
Hong Bo Ji
Keyword(s):  
Frequency Shift ◽  
Bond Length ◽  
Electron Density ◽  
Electrostatic Interaction ◽  
Theoretical Study ◽  
Blue Shift ◽  
Length Change ◽  
Red Shift ◽  
P Value ◽  
Small Contribution

The H bonds of HArF and HF with N2, CO, and BF were studied at the MP2(full)/6-311++G(2d, 2p) level. The results show that only the complexes WY···HArF (WY = N2, OC) and WY···HF (WY = N2, OC, FB) are stable, the H-bonding WY···HArF leads to contraction of the HAr bond with a concomitant frequency blue shift, but the H-bonding WY···HF causes the HF bond to elongate with a frequency red shift. A quantity P is defined to measure polarization of the HX bond; the H bonding causes the P value of the HX bond (X = Ar, F) to increase. The HX bond length change and frequency shift in the H-bonding WY···HArF and WY···HF are mainly caused by intermolecular hyperconjugation, n(Y) → σ*(HX) (X = Ar, F), where electrostatic interaction has only a small contribution. In HArF, the strong intramolecular hyperconjugation, n(F) → σ*(HAr), can adjust electron density on σ*(HAr); upon formation of H bonding, the HAr stretching frequency blue shift is caused by a decrease of intramolecular hyperconjugation and an increase of the s character of the Ar hybrid in the HAr bond, induced by the intermolecular hyperconjugation. In the H bonds of HF without intramolecular hyperconjugation, the intermolecular hyperconjugation, n(Y) → σ*(HF), leads to a red shift of the HF bond, although there is also large rehybridization.

Electrostatics determine vibrational frequency shifts in hydrogen bonded complexes

2014 ◽  
Vol 16 (46) ◽  
pp. 25247-25250 ◽  
Author(s):  
Arghya Dey ◽  
Sohidul Islam Mondal ◽  
Saumik Sen ◽  
Debashree Ghosh ◽  
G. Naresh Patwari
Keyword(s):  
Vibrational Frequency ◽  
Stabilization Energy ◽  
Frequency Shifts ◽  
Electrostatic Component ◽  
Stretching Vibration ◽  
Bonded Complexes ◽  
Hydrogen Bonded ◽  
Vibrational Frequency Shifts

The shifts in the acetylenic C–H stretching vibration in the C–H⋯X hydrogen-bonded complexes correlate with the electrostatic component of the stabilization energy.

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