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Title: Unique determination of the -CN group tilt angle in Langmuir monolayers using sum-frequency polarization null angle and phase

The relative phase and amplitude ratio between the ssp and ppp polarization combinations of the vibrational sum-frequency generation (SFG) response can be uniquely and accurately determined by the polarization null angle (PNA) method. In this report we show that PNA measurements of the -CN vibration in the 4-n pentyl-4'-cyanoterphenyl (5CT) Langmuir monolayer at the air/water interface yields ssp and ppp response of the same phase, while those in the 4-n-octyl-4'cyanobiphenyl (8CB) Langmuir monolayer have the opposite phase. Accordingly, the -CN group in the 5CT monolayer is tilted around 25+/-2 from the interface normal, while that in the 8CB is tilted around 57+/-2, consistent with the significant differences in the phase diagrams and hydrogen bonding SFG spectra of the two Langmuir monolayers as reported in the literature. These results also demonstrate that in SFG studies the relative phase information of the different polarization combinations, especially for the ssp and ppp, is important in the unique determination of the tilt angle and conformation of a molecular group at the interface.
Publication Date:
OSTI Identifier:
Report Number(s):
47760; KP1704020
DOE Contract Number:
Resource Type:
Journal Article
Resource Relation:
Journal Name: Chemical Physics Letters, 585:42-48
Research Org:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org:
Country of Publication:
United States
Polarization; vibrational sum-frequency generation; monolayer; hydrogen; Langmuir; interface; Environmental Molecular Sciences Laboratory