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Quantum Mechanics and Atomic Structure

Hana Alicic Chemistry 155 AB March 1, 2011

Introduction: Though prisms can be used to separate light into its component wavelengths, the process is much more successful when gratings are used. Gratings consist of surfaces containing closelyspaced grooves or lines that diffract each wavelength of light differently. Evidence of lights wavelike behavior comes from its interactions with gratings: when waves of light pass through these gratings, they break up into smaller waves that then experience constructive and destructive interference. The areas of constructive interference can be determined via the diffraction equation: n = dsin() in which d is the spacing between openings, is the angle of diffraction, and n corresponds to the order of the wave and is a whole number. If the wavelength is about of the grating spacing, then diffraction effects will be seen. Too small of a wavelength results barely noticeable diffraction while too large means that the wave will not pass through the grating at all. With light, a short wavelength (such as that of x-rays) is needed to pass through the close spacing between atoms in a solid. When using visible light, the correct grating must be chosen. In this experiment, we calculated for the grating constant, measured in lines/mm. A spectroscope was also utilized in the lab so that the stream of light was well-defined and the angle of diffraction was thus easy to determine. In this instrument, light first passes through a slit so as to hone its shape. The light is then passed through a grating and the resulting lines are measured. A ruler within the spectroscope is used to assign different wavelengths to each line. In the following section of the experiment, we examined the characteristic spectrums of light emitted by atoms. Because different atoms emit the same spectrum, despite being combined

with other atoms, emission spectrums can be used to identify elements. The Rydberg equation is used to determine the spectrum emitted by atoms. The equation connects energy levels to wavelengths: 1/ = R((1/nf2)-(1/ni2)) Where nf and ni are the principle quantum numbers and R is the Rydberg constant. The energy levels of one-electron ions are determined by Bohrs expansion of the Ryberg equation, in which each side of the proceding equation is multiplied by hc and the atomic number of the orbital is considered so that E = -2.18x10-18Z2((1/nf2)-(1/ni2)) As a result, one-electron atoms can only absorb or emit electrons with energy levels equivalent to those predicted by the quantum model (the difference between two quantum numbers). By determining the wavelengths associated with various metal ions, we were able to use the emission lines of an unknown ion to identify it. The final section of the experiment involved various dyes with delocalized bonds that could be modeled using the particle in a box. These compounds absorb visible light and as a result their ground state electrons transition to an excited state. The presence of these bonds means that it can be assumed that the potential energy of the molecule is constant throughout and then rises infinitely at the edges of the box (at each nitrogen). The energy change of an electron that absorbs light can be found using E = h2/8mL2(nf2-ni2) In which L is the length of the box from one nitrogen to the other. Since the Pauli Exclusion Principle says that only 2 electrons can occupy and given energy level, the highest occupied energy level can be determined to be N/@2+1 (nf). As a result, the formula becomes

E = h2/8mL2(N+1) If each carbon atoms contributes one electron to the system, then the N value will be p+3 (with the three electrons being contributed by nitrogen). When an electron is excited, the L value will become (p+3)(l), with l being a characteristic bond length. This signifies that the electron can travel between the two nitrogens as well as one bond length between each nitrogen. The l value is usually that of benzene, or 1.39 pm. Thus, E = ((h2)(p+4))/(8ml2(p+3)2) Since the potential at the ends of the change can be lowered due to attached chemical groups, a correction parameter must be introduced so that = ((8mcl2)(p+3+)2)/(h(p+4)) Methods: Measuring the Grating Constant Using the distance between the grating and wall (L) and the distance between the visible lines (d), the values was found. Then, using a wavelength of 632.8 nm, the grating constant was determined. Atomic Spectra and Transitions Between Energy States Initially, the spectroscope was calibrated by using the light from a mercury lamp and determining the locations of the spectral lines. Then, the spectroscope was used to find the wavelengths in the hydrogen emission spectrum. Flame tests were then used to ascertain the emission lines of various metal ions. Particle in a Box

The maximum absorbances and wavelengths of various dyes were determined using a spectrometer. Sunlight and the spectroscope were then used to find the absorbance lines of the dyes.

Results: Initially, the diffraction grating was determined to be 550 lines/mm. Figure 1: Determined using the emission spectrum of the mercury lamp, this graph was used to calucalte the wavelengths of the hydrogen and metal ions used later in the experiment.

800 700
Wavelength (nm)

Calibration of the Spectroscope

600 500
400 300

200 100 0 4 4.5 5 5.5 6 Displacement

y = 89.244x + 42.26 R = 0.9993



Figure 2: Using the set in which nf = 2 results in the largest R2 value and thus the best fit for the hydrogen emission spectrum.

Best Fit For Hydrogen Emission Spectrum

0.003 0.0025

0.0015 0.001
0.0005 0 y = -0.0107x + 0.0027 R = 0.9989



0.06 n(i)^-2




Table 1: A comparison of slope, intercept, R^2, and n(f) values for different sets of n(i) values for the hydrogen emission spectrum. The bolded section is for the best fit curve.

n(i) = 2,3,4,5 n(i) = 3,4,5,6 n(i) = 4,5,6,7 slope -0.0042 -0.0107 -0.0213 intercept 0.0025 0.0027 0.0029 R^2 0.9957 0.9989 0.9934 n(f) 2.095 2.016 1.945
Table 2: Using 2 as the value of nf for the hydrogen emission spectrum, the changes in energy between each of the lines were determined.

n(i) 3 4 5 6

E (J) -3.0278E-19 -4.0875E-19 -4.578E-19 -4.844E-19

The ionization potential for the hydrogen atom was found to be 5.45*10-19 J. To identify the unknown, we determined that its emission spectrum most resembled a mixture of strontium and lithium. However, it predominantly resembled strontium. Table 3: The emission spectrums for an unknown and the two metal ions most resembling the unknown, found using flame tests and a spectroscope.
Emission Spectrum for an Unknown Emission spectrum for Strontium Emission Spectrum for Lithium Displacements Wavelenths (nm) Displacements Wavelengths (nm) Displacements Wavelengths (nm) 4.6 452.7824 4.7 461.7068 5 488.48 5.6 542.0264 5.6 542.0264 5.4 524.1776 6.1 586.6484 6.1 586.6484 5.6 542.0264 6.3 604.4972 6.3 604.4972 6.1 613.4216 7.1 675.8924 7 666.968 6.4 586.6484 7.1 675.8924

Table 4: The values for the for four differing polymethine molecules, determined using p values characteristic of each molecule.

Molecule 3,3'-Diethylthiacyanine iodide 3,3'-Diethylthiacarbocyanine iodide 3,3'-Diethylthiadicarbocyanine iodide 3,3'-Diethylthiatricarbocyanine iodide

0.823 0.892 0.631 0.466

Discussion: The light from each of the flames was effectively split into its constituent wavelengths thanks to large number of lines (550) per each mm in the grating. This heavy concentration of lines meant that the lights of waves broke into smaller waves that then experience constructive and destructive interference. In the case of microwaves, their location at the lower end of the electromagnetic spectrum means that their wavelengths are relatively long (around 10-2 m). As a result, a screen acts as an effective block to the emission of the waves from within the microwave oven: the wavelengths are too large to pass through the gaps between the atoms in the solid. This occurs whenever the equation dsin = n is used and the /d value is greater than one. In that case, no n value can be used to solve the equation (as sin on its own cannot be greater than one) and the wave will not pass through the grating. Your body will not heat when standing next to a microwave as the few waves that are released will have such low energy so as to have no noticeable effect. In determining the calibration of the spectroscope, the wavelengths we saw for the emission lines of the mercury lamp differed from the expected values. The greatest difference was seen for the red emission line. Our value was 7.3 while the expected was 6.91, a difference of 0.39. This could have resulted from the red line being nearer to the edge of our vision and thus being more difficult to accurately determine. The emission spectrum of the hydrogen clearly revealed that the nf value for hydrogen was 2: the graph for the set of data in which ni=3,4,5,6 and nf= 2 was the best fit, with an r2 value of 0.9989. Determining the emission spectrum for an unknown sample proved more difficult as

the emission lines of the different metal ions were oftentimes very similar and differentiating the lines accurately was difficult. Furthermore, the unknown sample appeared to be contaminated and seemed to contain more than one ion. Its emission spectrum as well as its color was very similar to that of strontium, but we also determined that it had traits of lithium. Had the temperature of the flame been higher, the intensity of each of the emission lines would have been higher and the experiment would have been easier to perform. An increase in temperature means that more electrons have sufficient energy to switch between quantum levels, thus increasing the intensity. The more intense lines of color would be easier to identify. Our calculated value for the ionization energy of hydrogen was 5.45*10-19 J while the accepted value is equal to Rydbergs constant (2.18*10-18 J). This discrepancy is accounted for by the fact that we assumed our nf to be 2 while calculations for the ionization energy assume this same value to be 1 (the hydrogen is ionized from the ground state). Thus, our value was of the literature value. The value of the polymethine molecules decreased as the value of p increased (the molecules became larger). This correction parameter shows that the effect of the attached chemical groups on the larger molecules is less drastic than it is for the smaller ones. Because the percentage change of the length resulting from adding chemical groups to the end of a longer chain will be less than that of adding groups to a shorter chain, the alpha value for the longer chain will be smaller. Using the equation for the particle in the box, E = h2n2/8mL2 And the fact that E = hc/, it can be determined that as the length of the box increases, the wavelength of light increases. This is also supported by the equation

= 8mcl2(p+3+)3/h(p+4) in which the l value is related to the L value by L= l(p+3). This trend was seen in the lab, with the largest molecule, 3,3-diethyltricarbocyanine iodide, emitting the longest wavelength of the four. If the value was equal to zero, the situation would be ideal and the potential at the ends of the chain would be equal to infinity so that there would be no chance of the box size increasing. The equation for the wavelength values would be the same as seen before, but with no value considered. The values from the experiment are not exactly what would be expected for the particle in a box due to the attaching of chemical groups at the ends. However, the same trend is seen, with emitted wavelengths increasing as the molecule sizes increase. In finding the wavelengths of the dyes, there did not seem to be a correlation between the chain length and the percentage error in our data. The percentage errors varied in a nonlinear fashion and were so small (0.719% at most) that they suggested that our data was accurate. The absorbance values that we found for the dyes via the spectrometer were supported by using the spectroscope to view the dyes against sunlight. The absorbance spectrum seen in this manner did not include the maximum absorbances of the dyes. For example, the light blue dye had a maximum absorbance of 762 nm, a value not included on the absorbance spectrum of 3.8-5.5. Conclusion: The experiment showed various practical applications of quantum theory. The spectroscope was used in determining chemical characteristics as well as in supporting the wavelike behavior of light. The fact that light can be diffracted into varying wavelengths that

then interact in a way identical to other waves is a crucial support for quantum theory. The emission spectrums of chemicals support the idea of quantum orbitals in atoms. The fact that each transition between quantum levels releases a distinct wavelength of light (that can be determined using a spectroscope) and thus a distinct amount of energy illustrates the idea of discrete energies. Quantized energy levels are also seen with respect to particles in a box, with delocalized bonds transitioning and releasing various wavelengths. The larger the molecule, the longer the wavelength of light released as determined by the particle in a box equation. These aspects of quantum theory can be applied to identifying chemicals or at least determining their size via the analysis of the light that they emit or absorb.