foundations of spectroscopy Flashcards

(31 cards)

1
Q

spectroscopy definition

A

the study of how EM radiation interacts with matter

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2
Q

give 5 uses of spectroscopy

A
  • identification of molecules
  • checking success of reactions
  • checking purity
  • determining molecular properties/structure
  • quantitative analysis
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3
Q

spectrum definition

A

a plot of energy of excitation vs absorption, transmission or emission

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4
Q

absorption definition

A

measures amount of radiation absorbed/taken in depending on wavelength

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5
Q

transmission definition

A

measures amount of radiation transmitted/passed through depending on wavelength

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6
Q

emission definition

A

measures amount and wavelength of radiaiton emitted/released by a molecule following irradiation

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7
Q

wavelength, λ definition

A

distance between successive waves
units = m

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8
Q

frequency, v definition

A

number of waves per second
units = 2^-1 or Hz

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9
Q

wave number definition

A

= 1/λ , number of waves per metre
units = m^-1

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10
Q

what is the velocity of a wave?

A

= frequency x wavelength = speed of light
2.997x10^8 ms^-1

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11
Q

what are the 5 energy stores that make up total energy in a molecule?

A

translational (motion of whole molecule)
nuclear spin (changes in spin of electrons/protons)
rotational (rotation of molecule)
vibrational (motion of bonds between atoms)
electronic (movement of electrons between levels)

ΔE increases from translational (tiny ΔE) to electronic (large ΔE)

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12
Q

what is the born-oppenheimer approximation?

A

the assumption that the energy stores in a molecule are independent of each other

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13
Q

explain why the idea of quanitisation is fundamental to spectroscopy

A

energy of EM radiation is quantised, meaning it takes discrete values carried by photons
energy can only be released/absorbed in small packets (photons)
electrons can only occupy certain energy levels

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14
Q

snapshot definition

A

when measurement time is faster than process being measured e.g. electronic spectroscopy gives snapshots
- usually many molecules are being observed
so spectra produced in a combination of snapshots of each molecules electronic / vibrational / etc properties

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15
Q

average definition

A

when measurement time is slower than process being measured - as usually molecules are undergoing dynamic processes e.g. NMR gives an average
- lowering temp may allow a snapshot to be taken in process becomes slower than measurement timescale

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16
Q

how can electrons move between energy levels?

A

the molecules must absorb or emit a photon of equal energy to the gap between the initial energy level and the new energy level

17
Q

absorption spectra definition

A

molecules absorb photons with energy corresponding to energy level differences, the electron moves to a higher energy level

18
Q

emission spectra definition

A

molecules emit photons with energy corresponding to energy level differences, the electron moves to a lower energy level
e.g. atomic spectra

19
Q

what does absorption depend on?

A

absorption is related to the number of molecules in a particular energy level which can be promoted to the next state by absorbing a photon

20
Q

what does intensity of peaks depend on?

A

occupancy/population and degeneracy
this is because if more molecules are at a particular energy level then more molecules will be able to absorb a specific photon and be promoted, if levels are degenerate more molecules can occupy the same state, or undergo transitions equal to the same photon energy

21
Q

occupancy/population definition

A

number of molecules in each state

22
Q

degeneracy definition

A

levels with the exact same energy within a molecule

23
Q

what condition affects occupancy + why?

A

temperature dependent
at room temperature it is unlikely than all molecules are in the lowest state, but also few molecules will be in high energy states, molecules will occupy a range of energy levels depending on available thermal energy, or size of ΔE

24
Q

how does the boltzmann distribution link to spectroscopy?

A

it tells us that the intensity of absorption peaks depends on the number of molecules that absorb the radiation (aka the population)

25
analyse the graph given by population boltzmann equation
the graph is a downwards exponential exponential term is -ΔE/KbT the y-axis = n(upper)/n(lower) fraction it starts at (0,1) because e^0=1, meaning as exponential term tends towards 0 the population of upper and lower levels is approximately equal meaning -ΔE is very small or T is very large as exponential term gets larger the graph tends towards 0 as e^-infinity=0, meaning population of upper levels << lower levels meaning -ΔE us very large or T is very small simply, population falls off exponentially as ΔE increases
26
what is distribution of energy levels like if T is large?
at higher temp there is a higher population of energy levels
27
what is distribution of energy levels like if ΔE is large?
only lower energy levels will have significant populations, unless temperature is very high
28
what is distribution of energy levels like if ΔE is small?
many higher energy levels will be populated even at moderate temps
29
how does the addition of g(upper)/g(lower) pre exponential term change the equation?
this term is degeneracy of upper/lower levels, degeneracy must be taken into account to fully describe the pattern of intensity now if ΔE <
30
what impact does temperature have on degeneracy?
for 2 levels with the same degeneracy, as T gets larger populations of upper and lower level becomes the same, but the upper level can never have a higher population than the lower state in a fully thermal distribution
31
how does the type of transition that can take place depend on temperature?
electronic/UV-Vis > vibrational/IR > rotational/microwave