advanced molecular spectroscopy pt 2 (raman & derivative) Flashcards

1
Q

In raman, incident photons are scattered by molecules with what?

A

both an increased or decreased energy which is characteristic of sample

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2
Q

Scattering of incident photons are at what angles?

A

right angles

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3
Q

What is the energy change equal to?

A

difference in energy between vibrational energy levels

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4
Q

what does the energy change correspond to?

A

wavelengths in mid-infrared

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5
Q

what 3 ways can light interact with substance?

A

absorbed, transmitted, scattered

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6
Q

what are the ways that radiation can be scattered?

A

elastically or inelastically

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7
Q

If it is scattered elastically, how does this affect wavelength? and what is it called?

A

no change in wavelength, called rayleigh scattering

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8
Q

what is it called when radiation is scattered inelastically?

A

raman effect

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9
Q

Where does rayleigh scattering occur? how intense is the peak?

A

at exact wavelength of excitation - most intense peak

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10
Q

Between stokes and antistokes lines, which has greater and smaller energy than rayleigh peak? and which has longer/shorter wavelengths?

A

stokes = smaller, longer antistokes = greater, shorter

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11
Q

how intense are the stokes and antistokes lines?

A

stokes less intense than rayleigh, antistokes even weaker

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12
Q

What are virtual states?

A

assumed state of photon and molecule during short time period

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13
Q

A molecule will only emit monochromatic light and produce raman shifted lines (stokes and antistokes) when what occurs?

A

when molecule vibrates so that polarizability is changed during vibration

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14
Q

Raman ………… shift = infrared ………… peak frequency

A

frequency, absorption

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15
Q

Scattering involves a momentary distortion of what?

A

electrons distributed around a bond

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16
Q

What happens to the molecule in its distorted form? 2

A

it is temporarily polarised, ie develops a momentary induced dipole

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17
Q

This deforms molcules, leading to what?

A

vibrations with characteristic frequency

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18
Q

When there is no dipole moment in equilibrium position or when stretched, what does this mean?

A

no infrared absorption

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19
Q

If the polarizability varies, what does this mean?

A

it is raman active

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20
Q

In symmetric and anti symmetric modes of stretching, what happens to the dipole moment?

A

symmetric = no dipole moment, antisymmetric = dipole moment fluctuates

21
Q

Are symmetricand antisymmetric modes IR active or inactive?

A

symmetric - inactive, antisymmetric - active

22
Q

Describe the polarizability of symmetric and anti-symmetric stretching modes?

A

symmetric = polarizability fluctuates in phase with vibration, antisymmetric = polarizability of one bond increases as other decreases

23
Q

Are symmetric and antisymmetric stretching modes raman active or inactive?

A

symmetric = raman active, antisymmetric = raman inactive

24
Q

does raman require a special sample prep method?

A

no

25
Q

Why does water show up on raman and not usually on FTIR?

A

no background problem in raman

26
Q

what types of cell might be used in raman?

A

inexpensive glass or quartz

27
Q

what types of probes ideally used? 2

A

non-invasive and immersion probes

28
Q

Which spectra is less cluttered, raman or FTIR?

A

raman

29
Q

What makes this technique well suited for both organic and inorganic species?

A

spectral range is below 400cm-1

30
Q

What can be used to do a remote analysis in raman?

A

fibre optic cables

31
Q

A major limitation of raman is background signals arising - what causes this?

A

signal arising from fluorescence of analyte or impurities

32
Q

Is raman strong or weak effect?

A

weak

33
Q

incident flux of … photons will give 1 raman ……

A

10^8, photon

34
Q

A ppm impurity with a quantum yield of …. will give ….. fluorescence photons for the same flux

A

0.1, 10

35
Q

What range are the detection limits in?

A

parts per thousand

36
Q

How can this problem be eliminated?

A

using FT-Raman

37
Q

It uses a high power Nd-YAG laser at what wavelength?

A

1064nm

38
Q

Is raman more/less expensive than FTIR?

A

more, due to expensive laser and filters

39
Q

What are 2 advantages of FT-Raman over dispersive?

A

1064nm eliminates fluorescence and photodecomposition, superior frequency precision

40
Q

What is a disadvantage of FT-Raman over dispersive?

A

Water absorbs in the 1000nm region

41
Q

What 2 ways can raman be enhanced?

A

resonance raman effect, surface-enhanced raman spectroscopy (SERS)

42
Q

In resonance raman effect, how are the raman signals greatly enhanced?

A

by exciting with wavelength near electronic absorption peak

43
Q

how does this differ from fluorescence?

A

no vibrational relaxation

44
Q

how is this limited?

A

due to fluorescence of analyte or impurities

45
Q

Where are samples adsorbed in SERS?

A

on surface of collodial metal particles

46
Q

When combined with resonance raman, how much is enhancement increased by?

A

100x

47
Q

Name 2 applications of raman?

A

fingerprinting, paint analysis

48
Q

What is derivative spectroscopy used for?

A

removing spectral interferences and increasing selectivity

49
Q
A