In situ AC nanocalorimetry was used to characterize vapor-deposited glasses of six mono- and di-alcohol molecules. Benzyl alcohol glasses with high kinetic stability and decreased heat capacity were prepared. When annealed above the glass transition temperature T, transformation of these glasses into the supercooled liquid took 10 times longer than the supercooled liquid relaxation time (τ). This kinetic stability is similar to other highly stable organic glasses prepared by vapor deposition and is the first clear demonstration of an alcohol forming a stable glass. Vapor deposited glasses of five other alcohols exhibited moderate or low kinetic stability with isothermal transformation times ranging from 10 to 10 τ. This wide range of kinetic stabilities is useful for investigating the factors that control stable glass formation. Using our current results and literature data, we compare the kinetic stability of vapor deposited glasses prepared from 14 molecules and find a correlation with the value of τ at 1.25 T. We also observe that some vapor-deposited glasses exhibit decreased heat capacity without increased kinetic stability.

Spectroscopic ellipsometry was used to characterize vapor-deposited glasses of ethylbenzene (T g = 115.7 K). For this system, previous calorimetric experiments have established that a transition to the ideal glass state is expected to occur near 101 K (the Kauzmann temperature, T K) if the low-temperature supercooled liquid has the properties expected based upon extrapolation from above T g. Ethylbenzene glasses were vapor-deposited at substrate temperatures between 100 (∼0.86 T g) and 116 K (∼T g), using deposition rates of 0.02–2.1 nm/s. Down to 103 K, glasses prepared in the limit of low deposition rate have densities consistent with the extrapolated supercooled liquid. The highest density glass is within 0.15% of the density expected for the ideal glass. These results support the hypothesis that the extrapolated properties of supercooled ethylbenzene are correct to within just a few Kelvin of T K, consistent with the existence of a phase transition to an ideal glass state at T K.

In situ interdigitated electrode broadband dielectric spectroscopy was used to characterize the excess wing relaxations in vapor-deposited and aged glasses of methyl-m-toluate (MMT, Tg = 170 K). MMT displays typical excess wing relaxations in dielectric spectra of its supercooled liquid and glasses. Physical vapor deposition produced glasses with degrees of suppression of the excess wing relaxation that varied systematically with deposition conditions, up to a maximum suppression of more than a factor of 3. The glass deposited at a relatively high temperature, 0.96 Tg (163 K), showed the same amount of suppression as that of a liquid-cooled glass aged to equilibrium at this temperature. The suppression of the excess wing relaxation was strongly correlated with the kinetic stability of the vapor-deposited glasses. Comparisons with aged MMT glasses allowed an estimate of the structural relaxation time of the vapor-deposited glasses. The dependence of the estimated structural relaxation times upon the substrate temperature was found to be stronger than Arrhenius but weaker than Vogel-Fulcher-Tammann dependence predicted from extrapolation of relaxation times in the supercooled liquid. Additionally, this work provides the first example of the separation of primary and secondary relaxations using physical vapor deposition.

Previous work has shown that vapor-deposition can prepare organic glasses with extremely high kinetic stabilities and other properties that would be expected from liquid-cooled glasses only after aging for thousands of years or more. However, recent reports have shown that some molecules form vapor-deposited glasses with only limited kinetic stability when prepared using conditions expected to yield a stable glass. In this work, we vapor deposit glasses of 2-ethyl-1-hexanol over a wide range of deposition rates and test several hypotheses for why this molecule does not form highly stable glasses under normal deposition conditions. The kinetic stability of 2-ethyl-1-hexanol glasses is found to be highly dependent on the deposition rate. For deposition at T = 0.90 T, the kinetic stability increases by 3 orders of magnitude (as measured by isothermal transformation times) when the deposition rate is decreased from 0.2 nm/s to 0.005 nm/s. We also find that, for the same preparation time, a vapor-deposited glass has much more kinetic stability than an aged liquid-cooled glass. Our results support the hypothesis that the formation of highly stable 2-ethyl-1-hexanol glasses is inhibited by limited surface mobility. We compare our deposition rate experiments to similar ones performed with ethylcyclohexane (which readily forms glasses of high kinetic stability); we estimate that the surface mobility of 2-ethyl-1-hexanol is more than 4 orders of magnitude less than that of ethylcyclohexane at 0.85 T.

This article describes a graduate student-led effort to develop a climate survey to assess, advocate for, and improve the well-being and mental health of graduate students and postdocs in the Department of Chemistry at the University of Wisconsin−Madison. Graduate students have an increased incidence of depression relative to the general population, and given the transient nature of the student population, understanding and addressing mental health concerns can be challenging. The goal of this article is to illustrate how students, with the support of departmental faculty, staff, and existing on-campus mental health resources, can take the lead to investigate and assess issues related to the challenging graduate school environment. We describe the student-led development and implementation of and the subsequent follow-up to a department-wide survey aimed at destigmatizing the subject of mental health and fostering a more supportive community. This article serves as a framework to assist other interested and motivated graduate students who, with the support of local faculty, wish to develop and initiate a similar process in their own departments. We demonstrate that student-led actions can effectively tackle department-level problems and encourage other interested students to initiate a similar effort.

In situ AC nanocalorimetry was used to characterize vapor-deposited glasses of three phosphates with increasing lengths of alkyl side chains: trimethyl phosphate, triethyl phosphate, and tributyl phosphate. The as-deposited glasses were assessed in terms of their reversing heat capacity, onset temperature, and isothermal transformation time. Glasses with a range of kinetic stabilities were prepared, including kinetically stable glasses, as indicated by high onset temperatures and long transformation times. Trimethyl phosphate forms kinetically stable glasses, similar to many other organic molecules, while triethyl phosphate and tributyl phosphate do not. Triethyl phosphate and tributyl phosphate present the first examples of non-hydrogen bonding systems that are unable to form stable glasses via vapor deposition at 0.2 nm/s. Based on experiments utilizing different deposition rates, we conclude that triethyl phosphate and tributyl phosphate lack the surface mobility required for stable glass formation. This may be related to their high enthalpies of vaporization and the internal structure of the liquid state.

In situ AC nanocalorimetry and dielectric spectroscopy were used to analyze films of vapor-deposited triphenyl phosphite. The goal of this work was to investigate the properties of vapor-deposited glasses of this known polyamorphic system and to determine which liquid is formed when the glass is heated. We find that triphenyl phosphite forms a kinetically stable glass when prepared at substrate temperatures of 0.75–0.95Tg, where Tg is the glass transition temperature. Regardless of the substrate temperature utilized during deposition of triphenyl phosphite, heating a vapor-deposited glass always forms the ordinary supercooled liquid (liquid 1). The identity of liquid 1 was confirmed by both the calorimetric signal and the shape and position of the dielectric spectra. For the purposes of comparison, the glacial phase of triphenyl phosphite (liquid 2) was prepared by the conventional method of annealing liquid 1. We speculate that these new results and previous work on vapor deposition of other polyamorphic systems can be explained by the free surface structure being similar to one polyamorph even in a temperature regime where the other polyamorph is more thermodynamically stable in the bulk.