As most every person at this conference can appreciate, spectroscopy, especially at the undergraduate level, is often considered one of the most difficult subjects to undertake and, due to this mentality, is often avoided at all costs. To overcome this stigma and make the material resonate with undergraduates, it is important to give them avenues by which to actually get involved in the processes of spectroscopy. In this way, the students become invested in some aspect of the subject which is applicable to their own personal interests. At Missouri S&T, this is achieved in multiple ways. In the research lab, students are given tasks that align with their interest, but also achieve a common goal of a spectrometer enhancement or molecular target of interest in microwave spectroscopy. They are given the tools and instruction to succeed as well as the leeway to fail in a project as this is the cornerstone of discovery. When given this freedom, they become leads in a project, guided and mentored by both the graduate students and myself. If a student is interested in teaching, we have had undergraduates create physical chemistry labs and instruct them in order to guide other students through the process of learning, thereby augmenting their own knowledge. For expanded or more general undergraduate spectroscopy outreach, I serve as the physical chemistry lab instructor and the Associate Advisor of our university's Mars Rover Design Team, which always builds and implements an onboard spectrometer for field analyses. The overarching theme of the talk is to get students interested early and keep them involved. The university helps with this by having programs that will get the students involved as young as the high school level. How we have utilized these programs, reached, and kept student interest while also mitigating the costs of such endeavors at Missouri S&T will be discussed.

In undergraduate thermodynamics, entropy is one of the most misunderstood topics; in part, this is due to its abstract nature, but confusion also stems from using a definition based on “order” or lack thereof. Students can understand this definition easily, especially if it is related to the state of a messy room over the course of time. When asked about the entropy of a molecular system, however, students have difficulty translating their definition based on “order” to a new context. An activity was created and implemented in an undergraduate physical chemistry course to guide students through alternate definitions of entropy. The activity combines thermodynamic calculations, entropy, and current spectroscopic researchLeavitt, C. M.; Moore, K. B.; Raston, P. L.; Agarwal, J.; Moody, G. H.; Shirley, C. C.; Schaefer, H. F.; Douberly, G. E. Liquid Hot NAGMA Cooled to 0.4 K: Benchmark Thermochemistry of a Gas-Phase Peptide. J. Phys. Chem. A 2014, 118 (41), 9692–9700.ogether with concepts covered in class to give students a complete picture of this topic. In this talk, the activity and its implementation will be discussed along with preliminary outcomes.

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Footnotes:

Leavitt, C. M.; Moore, K. B.; Raston, P. L.; Agarwal, J.; Moody, G. H.; Shirley, C. C.; Schaefer, H. F.; Douberly, G. E. Liquid Hot NAGMA Cooled to 0.4 K: Benchmark Thermochemistry of a Gas-Phase Peptide. J. Phys. Chem. A 2014, 118 (41), 9692–9700.t

In molecular spectroscopy, our models of the molecular world are built on rigorous spectroscopic experimentation and rich interplay between theory and experiment. To instill such appreciation to undergraduate students, who have little experience in either spectroscopic experiments and theory, is challenging. We have developed a new computational laboratory component to complement the material covered in a senior undergraduate course on molecular spectroscopy. Specifically, we focus on illustrating molecular spectroscopic concepts (some of which can be quite abstract and complicated) taught in class with electronic structure calculations. This talk will describe our implementation and the learning outcome. Two particular examples will be discussed. One is related to the misconception that electron density is the main factor responsible for NMR chemical shifts and how we utilize both experimental data and calculations to help students overcome this common misconception. The other deals with differences in geometries, for example, those obtained using rotational constants directly, isotopic substitution procedures, and electronic structure calculations. This talk will also discuss how the above activities worked in practice and the improvements we plan to implement next time.

Spectroscopy is a fundamental component of physical chemistry courses. To encourage students to take more interest in the critical contributions of spectroscopic properties to the subject, I assign different molecules to the students. In the second semester of a two-semester course that covers statistical and classical thermodynamics, the students draw molecules from a hat on the first day of class. They look up spectroscopic properties for their molecules on the web and use the values in various homework, quiz, and exam problems. In a one semester "principles" course, they build a closed-shell molecule from a limited set of atoms. I then provide the students with calculated values of spectroscopic properties, which they use in a term project about their molecules that covers structure, spectra, partition functions, and properties derived from partition functions.

The microwave spectra of three unique chemicals have been measured and assigned for the first time. The spectra of 4-fluorophenol, 1-bromo-2-fluorobenzene, and 1-bromo-3-fluorobenzene were measured with a chirped-pulse Fourier transform microwave (CP-FTMW) spectrometer in the 8 – 18 GHz range. The spectrometer employs an Analog Devices AD-9914 direct digital synthesizer to generate a chirped pulse with a bandwidth of 1 GHz. The chirped pulse is mixed with a tunable carrier frequency and the spectrum is measured in 2 GHz (the output of the mixer includes the lower and upper sidebands) sections. Chemical samples are introduced through a small hole in a spherical mirror in order for the pulsed molecular beam to be coaxial with the microwave pulse. Experimental rotational parameters of the three chemical species will be presented along with a description of the spectrometer.

Ultrafast interfacial charge transfer (CT), charge separation (CS), and charge recombination (CR), are among the key factors in determining the overall efficiency of the organic photovoltaic devices. Perylene tetracarboxylic diimide (PDI) and its derivatives exhibit excellent thermal, chemical and optical stability, and highly absorbed in visible region. The combination of these features makes PDIs ideal molecular frameworks for development of a photovoltaic devices. Perylene tetracaroxylic diimides with appended diamine (PDI-EA), and two isomers of phosphonic acid-appended diakoxynapthalene derivatives (DAN) have been synthesized and their photophysical properties and self-assembly studied by using absorption and emission spectroscopic techniques. These complexes were designed for use as mimics of the photosynthetic reaction center. Self-assembly of these molecules in aqueous environment resulted in the formation of charge transfer (CT) complex. In polar solvent, the absorption and emission spectra were blue-shifted as the incremental addition of NAD. Further increasing DAN1 to PDI-EA ratio resulted in significant fluorescence quenching of the emission band, which can be assigned to fast electron transfer from DAN1 to singlet-excited state of PDI-EA.

The need to transition from hydrocarbon-based fuels to clean, economically feasible sources of energy is critically important toward meeting rapidly increasing global energy requirements and reducing CO₂ emission. Dye sensitized solar cells (DSSCs) are considered to be the potential candidates for the next generation of solar cells because of their ease of fabrication and efficiency over silicon based inorganic solar cells and tunable optical properties. DSSCs were fabricated using eight natural dyes extracted from blackberry, red beetroots, yellow beet roots, spinach, blueberry, cabbage, and turmeric in different solvents (ethanol, acetone, and water). The sensitization performance related to interaction between the dyes and the TiO₂ surface was discussed. Finally, photophysical properties and power-conversion efficiencies of each individual dye and the mixture of extracted dyes were evaluated.

The cyclohexadienyl radical (C₆H₇) was observed in a low temperature argon matrix with matrix isolation infrared spectroscopy. The C₆H₇ radical was produced from the reaction of H atoms with benzene (C₆H₆) in the argon matrices. The H atoms were produced by vacuum ultraviolet (VUV) photolysis of H₂S, which was co-deposited with the C₆H₆ in the argon matrices. The most intense peak of the C₆H₇ radical was observed at 621.0 cm⁻¹, with several other weaker peaks observed at 865.9, 910.9, 961.2, 973.7, 1290.3, 1390.2, 1394.9, 1425.9, 2758.7, and 2781.3 cm⁻¹. The experiments were performed with various concentrations of H₂S and C₆H₆ and at deposition temperatures of 10 K, 15 K, and 20 K. The largest yield of the C₆H₇ radical was for VUV photolysis co-deposition of 1:200 H₂S:Ar with 1:200 C₆H₆:Ar at 15 K. The identification and assignment of the C₆H₇ radical peaks was accomplished by comparisons to spectra without VUV photolysis, the H₂S and C₆H₆ monomer spectra both with and without VUV photolysis, filtered (400 – 900 nm) Hg-Xe lamp photolysis, and 35 K annealing spectra. Experiments were also performed in which H atoms were reacted with C₆D₆ producing the C₆D₆H radical, with peaks observed at 460.0, 747.8, 759.3, 830.0, 1245.6, 1246.7, and 2791.9/2797.0 cm⁻¹. Quantum chemistry calculations for the C₆H₇ radical were also performed using density functional theory at the B3LYP/aug-cc-pVTZ level to obtain the theoretical structure and theoretical infrared spectrum to support the assignments. The peaks of the C₆H₇ radical observed in argon matrices are in good agreement with the values reported in xenon matricesV. I. Feldman, F. F. Sukhov, E. A. Logacheva, A. Y. Orlov, I. V. Tyulpina, and D. A. Tyurin, Chem. Phys. Lett. 437, 207 (2007)nd para-hydrogen matricesM. Bahou, Y. J. Wu, and Y. P. Lee, J. Chem. Phys. 136, 154304 (2012)

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Footnotes:

V. I. Feldman, F. F. Sukhov, E. A. Logacheva, A. Y. Orlov, I. V. Tyulpina, and D. A. Tyurin, Chem. Phys. Lett. 437, 207 (2007)a M. Bahou, Y. J. Wu, and Y. P. Lee, J. Chem. Phys. 136, 154304 (2012).

Coherent multidimensional spectroscopy is one of the most powerful techniques that has been developed in recent years. In this talk, we describe how our undergraduate research group has created a series of high resolution coherent 2D and 3D spectroscopic techniques. These techniques have the ability to overcome severe spectral congestion commonly encountered in rotationally resolved molecular spectra. They can also automatically sort peaks by quantum number, species, and selection rule.