Polarization Modulation Infrared Reflectance Absorption Spectroscopy(PMIRRAS) Samantha Nania Shaw Group Meeting How it Works

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1 Polarization Modulation Infrared Reflectance Absorption Spectroscopy(PMIRRAS) Samantha Nania Shaw Group Meeting How it Works

2 What is PMIRRAS and why do we use it? A surface sensitive spectroscopy technique Less than 1 µm from surface Estimated from 1 4 or 1 2 of the wavelength of the incident radiation Modulation of the source gives both S- and P-polarized light Only molecular vibrations with some fraction of a dipole moment perpendicular to the surface are active molecular orientation Insensitive to atmospheric H 2 O and CO 2 in the vapor phase

3 Instrument set up IR Radiation Polarizer PEM Detector

4 Polarizer and PEM Made of piezoelectric transducer which is glue to ZnSe crystal Piezo element converts periodic voltage to a periodic mechanical wave Compresses or expands crystal Operates at 50 khz resonant frequency Half-retardation occurs at Compressed crystal (angle +45 ) Expanded crystal (angle -45 ) I OV I OH I l I D φ = I S + I P 2 I ly I l 45 I lx I S + I P I S 2 I P cos φ I D Zamlynny, V.; Lipkowski, J., In Advances in Electrochemical Science and Engineering, WILEY-VCH: Weinheim, 2006.

5 Instrument set up IR Radiation Polarizer PEM Detector

6 Surface Selection Rules Electric Field E p : parallel to surface normal Enhanced E s : perpendicular to surface normal Cancelled Only occurs on metals Allows for orientational studies hν i E p1 r E s1 i Y Z E p E i p1 E r s1 X hν r Zamlynny, V.; Lipkowski, J., In Advances in Electrochemical Science and Engineering, WILEY-VCH: Weinheim, 2006.

7 Instrument set up IR Radiation Polarizer PEM Detector

8 Mean Squared Electric Field Strength (MSEFS) MSEFS for the E p is maximized around 80 but drops off drastically from there MSEFS for E s is negligible at this angle Angle of Incidence Zamlynny, V.; Lipkowski, J., In Advances in Electrochemical Science and Engineering, WILEY-VCH: Weinheim, 2006.

9 Relevant Equations Law of reflection: θ 1 i = θ 1 r Snell s Law of refraction: n 2 sin θ 2 t = n 1 sin θ 1 i Fresnel Equations for reflection(r) and transmission(t) r r s = E s1 i = ξ 1 ξ 2 ξ 1 +ξ 2 E s1 t s = E s1 t Ei = 2ξ 1 s1 ξ 1 +ξ 2 where ξ j = n j cos θ j t = r r p = E p1 i = n 2 ξ 1 n 2 1 ξ 2 n^ 2 2 ξ 1 +n^ 2 1 ξ 2 E p1 t p = E t p1 E p1 ^ ^ ^ ^ ^ i = 2n 2 ξ 1 n 1 n^ 2 ξ 1 +n^ 2 1 ξ ^ 2 ^ n j 2 n 1 2 sin 2 θ 1 t ^ n 2 Zamlynny, V.; Lipkowski, J., In Advances in Electrochemical Science and Engineering, WILEY-VCH: Weinheim, 2006.

Sample Preparation and Pre-Data collection Dry surface with nitrogen and place in cell with dry capillary Pick wavelength on PEM controller that will allow your peaks to be near the max of the

10 Sample Preparation and Pre-Data collection Dry surface with nitrogen and place in cell with dry capillary Pick wavelength on PEM controller that will allow your peaks to be near the max of the Bessel function but still in the linear portion for easy base lining Alignment Want to optimize to get the focal point on the surface Check Peak to Peak (between 2-10) Under Experimental Setup- Bench

Function Move Switch from local and Sum to Ext and Diff Check External A in SST menu Experimental Setup- Bench- Single

11 Sample Preparation and Pre-Data collection Check Phase Plug in Phase cords from oscilloscope Adjust using knob on top left of SSD box Tip: Found best when the phase looks like that in the top image and the phase is at Check Bessel Function Move Switch from local and Sum to Ext and Diff Check External A in SST menu Experimental Setup- Bench- Single Beam Before you start collecting, Check Dual Channel Want A channel to be larger than B by adjusting gain knobs on SSD box

Wetting Take PMIRRAS and IRRAS of bare silver sample with nitrogen purge IRRAS will stand for a background for when doing saturation Saturate cell Turn off nitrogen Allowing drops to be dispensed

12 Wetting Take PMIRRAS and IRRAS of bare silver sample with nitrogen purge IRRAS will stand for a background for when doing saturation Saturate cell Turn off nitrogen Allowing drops to be dispensed from capillary to bottom of the cell Try not to squirt onto the sample for condensation layer studies Take IRRAS spectra since vapor phase is the crucial state Take PMIRRAS before wetting to analyze for condensation layer Start wetting

13 Ratio A and B channel to get spectra Once scan has finished, you need to ratio the spectra (SST menu) B A R R R p R s ( R R ) s p 2 Zamlynny, V.; Lipkowski, J., In Advances in Electrochemical Science and Engineering, WILEY-VCH: Weinheim, 2006.

14 Base lining To get rid of the Bessel function Process- Baseline Correct Put points along Bessel- BE CAREFUL around peaks

Chiroptical Spectroscopy

Chiroptical Spectroscopy Theory and Applications in Organic Chemistry Lecture 2: Polarized light Masters Level Class (181 041) Mondays, 8.15-9.45 am, NC 02/99 Wednesdays, 10.15-11.45 am, NC 02/99 28 Electromagnetic