On the correlation between bond-length change and vibrational frequency shift in halogen-bonded complexes

2011 ◽  
Vol 134 (22) ◽  
pp. 224303 ◽  
Author(s):  
Weizhou Wang ◽  
Yu Zhang ◽  
Baoming Ji ◽  
Anmin Tian
Keyword(s):  
Frequency Shift ◽  
Bond Length ◽  
Vibrational Frequency ◽  
Length Change ◽  
Bonded Complexes

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.

Vibrational frequency shift of HF in helium clusters: Quantum simulation and experiment

1996 ◽  
Vol 105 (19) ◽  
pp. 8666-8683 ◽  
Author(s):  
Dörte Blume ◽  
Marius Lewerenz ◽  
Friedrich Huisken ◽  
Michael Kaloudis
Keyword(s):  
Frequency Shift ◽  
Vibrational Frequency ◽  
Quantum Simulation ◽  
Helium Clusters ◽  
Simulation And Experiment
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