Experimental and calculated spectra of air/H2O

interface
Muhammet Mammetkuliyev

April 27, 2017

1 Results from MB-pol[13]

Figure 1: Z-axis is pointing towards air.

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2 Experimental and Calculated Spectra for Water
Bend region

Figure 2: Experimental and calculated spectra for water bend at air/H2O interface.
Experimental angles are 63 and 67 for IR and Vis (800 nm) light respectively.

Figure 3: Calculated SSP shifted by 40 cm-1 and calculated PPP spectra shifted by 50
cm-1.

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3 Experimental and Calculated Spectra for Water
Stretch region

Figure 4: Calculated spectra are obtained by multiplying (2) values (obtained from MB-
pol) with the fresnel factors. (2) values were shifted to the red by 175 cm1 to account
for nuclear quantum effect. Calculated free OH peak (3700 cm) is at 3665 cm-1 for ppp
and 3700 cm-1 for ssp polarizations.

Figure 5: Calculated SSP shifted by 175 cm-1 and calculated PPP spectra shifted by 140
cm-1.

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4 Comparison of Calculated Spectra to Published
Work

Shen et.al. PRL 86, 4799 (2001)

5 Orientational Analysis
Orientational analysis to find free OH and water bend angles wrt to surface normal is
described. To this end, calculated xxz , xzx and zzz will be used. For the water stretch
region, 4 lorentzians are fitted while for water bend region, two lorentzian are fitted. The
fitted equation is Eq. 73 and 78 from Lambert[5]. Lorentzian amplitude from fit is shown
in the table.

Free OH Bend (1630 cm-1) Bend (1670 cm-1)

xxz 38 2.28 0.2
xzx 1.75 2.1 0.3
zzz 78 1.05 0.38

For orientation function, ijk expressions from Hong-Fei paper[6] were used. Eq 23
for free OH and Eq 32 for water bend

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Figure 6: Orientational analysis for bend. The bend at 1670 cm-1 is oriented below 90
degrees while bend at 1630 cm-1 is oriented at an angle above 110 degrees. = 15
value used for gaussian distribution.

Figure 7: Orientational analysis for free OH (3700 cm-1). = 15 value used for gaussian
distribution.

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References
[1] Babin, V.; Medders, G. R.; Paesani, F First Principles Water Potential with Flexible Monomers.
II: Trimer Potential Energy Surface, Third Virial Coefficient, and Small Clusters J. Chem. Theory
Comput. 2014, 10, 1599-1607

[2] Babin, V.; Leforestier, C.; Paesani, F. Development of a First Principles Water Potential with
Flexible Monomers: Dimer Potential Energy Surface, VRT Spectrum, and Second Virial Coefficient.
J. Chem.Theory Comput. 2013, 9, 5395-5403

[3] Medders, G. R.; Babin, V.; Paesani, F. Development of a First Principles Water Potential with
Flexible Monomers. III. Liquid Phase Properties. J. Chem. Theory Comput. 2014, 10, 2906-2910.

[4] Xing Wei and Y. R. Shen Motional Effect in Surface Sum-Frequency Vibrational Spectroscopy PRL
2001, 86, 4799

[5] Alex G. Lambert, Paul B. Davies and David J. Neivandt Implementing the Theory of Sum Frequency
Generation Vibrational Spectroscopy: A Tutorial Review Applied Spectroscopy Reviews, 2005, 40:2,
103

[6] Hong-Fei Wang, Wei Gan, Rong Lu, Yi Rao and Bao-Hua Wu Quantitative spectral and orienta-
tional analysis in surface sum frequency generation vibrational spectroscopy International Reviews
in Physical Chemistry,2005, 24, 191-256