Jason Boettger Research Statement

The natural world is incredibly complex. Even more incredible is the relative simplicity
of natural laws that govern its behavior. There are only a few fundamental forces that govern the
properties and dynamics of all physical systems. This means we can investigate individual
components and extend our understanding to larger systems. Modeling is a good way to
combine quantitative understanding of small pieces into an understanding of the dynamics of a
larger system. My interest is in analyzing how the extremely small-scale interactions of
chemistry build up into the properties of geochemical interest.
In my research, I calculate the properties of small chemical systems ranging from a few
atoms to hundreds of atoms using molecular modeling, and apply that information to
understand their environmental behavior. My Ph.D. work focused on the chemical mechanism
of carbonate isotope fractionation, extending an understanding of hydrogen bonding during
carbonate formation to the origin of vital effects in coral carbon and oxygen isotope records. My
postdoc work focuses on prediction of position-specific and clumped isotope signatures in
organic compounds of geochemical interest, with the goal of unraveling a compound’s synthesis
and breakdown history through its isotope patterns. My research is well-suited to
undergraduate and graduate research, as it is highly modular and supports development of
chemical reasoning and 3D visualization skills.

Research Description
Paleoclimate proxies are necessary to contextualize current rates of change relative to the
past. Proxies need to reflect the environmental variable of interest through some causative
mechanism, not simple correlation. My work involves modeling the mechanism of isotope
proxies, to tease out the impact of climate and biological variables on noisy proxy records.
My PhD research focused on the C, O, and clumped isotope proxies in corals. These
proxies reflect carbon cycling and temperature in the tropical ocean over the past several
centuries with annual resolution. But there is a catch: the proxies do not only vary based on
these variables, but on a host of other processes, including biological influences termed “vital
effects”. I investigated the chemical basis for possible vital effect mechanisms: kinetic
fractionation during fast reaction of CO2 to form carbonate, and equilibrium fractionation based
on starting composition. I quantified the effects of hydrogen bonding on the processes: because
stronger bonds concentrate heavier isotopes, hydrogen bonding in the aqueous environment
within a coral alters the isotopic composition by changing the bond strength of the chemical
species and intermediates. I found that accuracy of calculated bond vibrations relative to those
measured by IR and Raman spectroscopy are a much better predictor of modeled fractionation
factor than other experimental properties, even the isotope shift in vibrations which form the
theoretical basis for fractionation. Hydrogen bonding strongly controls the final isotopic
composition, but the effect magnitude and even sign vary based on which atoms are donating or
accepting the hydrogen bond. These effects can have an impact on interpreted temperature of
>5oC per H-bond. My work suggests that models of isotope fractionation in other aqueous
systems can be improved in accuracy and accelerated in computation time by evaluation of
incremental effects of single H-bonds.
My postdoctoral research focuses on simultaneous prediction of multiple isotope signals
in various geochemical compounds, including organic ones, as part of the NASA Astrobiology
Center for Isotopologue Research (ACIR). I have published work on the influence of adsorption
on isotopic fractionation in nonpolar compounds, highlighting the importance of vibrational

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Jason Boettger

anharmonicity. I mentored a graduate student who ultimately published that modeling work in
conjunction with their own experimental and modeling work octane sorption on kaolinite. My
ongoing projects include prediction of equilibrium and kinetic fractionation in organic
compounds such as amino acids, evaluation of molecular modeling technique accuracy in
gaseous systems, pH-dependent Si and O isotope fractionation in silicates in aqueous
environments, reaction energetics of amino acid enantiomers during abiotic peptide formation,
and 34S-18O clumping in sulfates and the effect of laboratory sample preparation. Most of these
projects involve collaborations both inside and outside the ACIR team.
Modeling of equilibrium fractionation with molecular models is fairly straightforward
when using certain simplified representations of the local chemical environment in aqueous
systems. However, organic compounds, especially biogenic ones, are often formed under
disequilibrium conditions. Far from being inapplicable, the models’ equilibrium predictions
provide a baseline to interpret the extent of disequilibrium in the position-specific and clumped
isotope signals of organic molecules. The use of equilibrium models is necessary because atoms
with the lightest isotopic signature are not necessarily the most subject to kinetic fractionation,
as is often assumed.

Undergraduate Research and Teaching

My research is well-suited to undergraduate research for four main reasons: it is quick
and cheap, it is easily divided into small projects, it can be compared to simple laboratory data,
and it supplements chemistry education well. Well-crafted small calculations can run via open-
access software on a desktop computer over several days and give useful results, while larger
sets of calculations can run quickly on a supercomputer available to most universities. Project
sizes can be small: a sample undergraduate project might involve computing the interaction of
one molecule with one mineral surface in a handful of orientations, which would give more than
enough model results to compare with experimental data and present at a national conference.
Simple batch mixing experiments can be used to create synthetic samples, which when analyzed
using ICP-MS give a direct comparison to model results. Finally, in learning to perform the
calculations, students learn the underlying physics and thermodynamics that govern reactions
and their energetics. Students grapple with concepts like Gibbs free energy, activation energy,
and reaction kinetics while performing molecular modeling research. These principles are
foundational in a geochemical education. Students also interact with graphical visualizations of
their molecular systems, which can help them appreciate the atomic nature of even the most
complex environmental system. Molecular modeling is a cheap, digestible, and educational
endeavor for undergraduate researchers.
My research also informs my geochemistry teaching. I have built crystal structures of
common minerals using molecular visualization tools, which I incorporated into Physical
Geology labs to demonstrate the way microscopic mineral structure builds into macroscopic
crystal form and cleavage. I will do the same when teaching geochemistry, to demonstrate
concepts including activation energy, acid-base reactions, and molecular vibrations. This last
topic is particularly important, as it is fundamental to diverse geochemical situations including
infrared spectroscopy, greenhouse gases, zero point energy’s effect on Gibbs free energy, and
isotope fractionation. Visualization is key to learning in the geosciences, and my skill set enables
me to teach microscopic concepts that are especially difficult to visualize.