The Impacts of the Molecular Education and Research Consortium in Undergraduate Computational Chemistry on the Careers of Women in Computational Chemistry.

The Molecular Education and Research Consortium in Undergraduate Computational Chemistry (MERCURY) has supported a diverse group of faculty and students for over 20 years by providing computational resources as well as networking opportunities and professional support. The consortium comprises 38 faculty (42% women) at 34 different institutions, who have trained nearly 900 undergraduate students, more than two-thirds of whom identify as women and one-quarter identify as students of color. MERCURY provides a model for the support necessary for faculty to achieve professional advancement and career satisfaction. The range of experiences and expertise of the consortium members provides excellent networking opportunities that allow MERCURY faculty to support each other's teaching, research, and service needs, including generating meaningful scientific advancements and outcomes with undergraduate researchers as well as being leaders at the departmental, institutional, and national levels. While all MERCURY faculty benefit from these supports, the disproportionate number of women in the consortium, relative to their representation in computational sciences generally, produces a sizable impact on advancing women in the computational sciences. In this report, the women of MERCURY share how the consortium has benefited their careers and the careers of their students.

Using Diffusion Monte Carlo Wave Functions to Analyze the Vibrational Spectra of H7O3+ and H9O4.

An approach for evaluating spectra from ground state probability amplitudes (GSPA) obtained from diffusion Monte Carlo (DMC) simulations is extended to improve the description of excited state energies and allow for coupling among vibrational excited states. This approach is applied to studies of the protonated water trimer and tetramer, and their deuterated analogs. These ions provide models for solvated hydronium, and analysis of these spectra provides insights into spectral signatures of proton transfer in aqueous environments. In this approach, we obtain a separable set of internal coordinates from the DMC ground state probability amplitude. A basis is then developed from products of the DMC ground state wave function and low-order polynomials in these internal coordinates. This approach provides a compact basis in which the Hamiltonian and dipole moment matrix are evaluated and used to obtain the spectrum. The resulting spectra are in good agreement with experiment and in many cases provide comparable agreement to the results obtained using much larger basis sets. In addition, the compact basis allows for interpretation of the spectral features and how they evolve with cluster size and deuteration.

Evaluation of Matrix Elements Using Diffusion Monte Carlo Wave Functions.

Approaches for using diffusion Monte Carlo (DMC) to evaluate matrix elements involving two vibrational wave functions are explored. In the first part of this study, overlaps between a wave function obtained using DMC and one that can be calculated analytically are evaluated. In this case, the analytical wave function is used as the guiding function for an importance sampled DMC simulation. The accuracy of the calculated overlaps is found to depend strongly on the accuracy of the calculated descendant weights, which are obtained in the DMC simulation. While a single evaluation of the descendant weights is sufficient for obtaining projected probability amplitudes or expectation values of multiplicative operators, averages of multiple independent evaluations of the descendant weights are required to obtain accurate matrix elements. This approach is investigated for one-dimensional model systems as well as H2CO, H2D+, and D2H+. The approach is extended to the evaluation of matrix elements of the dipole moment operator between the ground state and states with one quantum of excitation in one of the OH stretching vibrations in H3O2-. For these calculations, the wave functions for both the ground and excited states are evaluated using DMC. The described methodology opens the possibility of evaluating matrix elements involving two different states, both of which are obtained using DMC.

Spectral signatures of proton delocalization in H+(H2O)n=1-4 ions.

Couplings involving large amplitude vibrations in H+(H2O)n (n = 1-4) are explored using several theoretical approaches. These include harmonic treatments, analysis of harmonically coupled anharmonic oscillator (HCAO) models of the OH stretching vibrations, vibrational perturbation theory (VPT2) in internal coordinates, and diffusion Monte Carlo (DMC). It is found that couplings between shared proton stretches and HOH bends can lead to normal modes that are significantly mixed in character. Couplings between the various OH stretching vibrations are much weaker, and the OH stretches are well-described by harmonically coupled anharmonic oscillator models. Anharmonic couplings and the role of these large amplitude vibrations are further explored using DMC and VPT2. Based on the results of these calculations, it is found that all of the H+(H2O)n ions considered in this study display several different types of large amplitude vibrational motions even in their ground states. In the case of H7O3+, degenerate VPT2 calculations indicate that there are large couplings between the shared proton stretch and various lower frequency vibrations that correspond to motions that break the ionic hydrogen bonds. This leads to vibrational eigenstates that have contributions from several zero-order states.

Photoinduced Plasmon-Driven Chemistry in trans-1,2-Bis(4-pyridyl)ethylene Gold Nanosphere Oligomers.

Continuous wave (CW) pump-probe surface-enhanced Raman spectroscopy (SERS) is used to examine a range of plasmon-driven chemical behavior in the molecular SERS signal of trans-1,2-bis(4-pyridyl)ethylene (BPE) adsorbed on individual Au nanosphere oligomers (viz., dimers, trimers, tetramers, etc.). Well-defined new transient modes are caused by high fluence CW pumping at 532 nm and are monitored on the seconds time scale using a low intensity CW probe field at 785 nm. Comparison of time-dependent density functional theory (TD-DFT) calculations with the experimental data leads to the conclusion that three independent chemical processes are operative: (1) plasmon-driven electron transfer to form the BPE anion radical; (2) BPE hopping between two adsorption sites; and (3) trans-to- cis-BPE isomerization. Resonance Raman and electron paramagnetic resonance (EPR) spectroscopy measurements provide further substantiation for the observation of an anion radical species formed via a plasmon-driven electron transfer reaction. Applications of these findings will greatly impact the design of novel plasmonic devices with the future ability to harness new and efficient energetic pathways for both chemical transformation and photocatalysis at the nanoscale level.

Probing Intermolecular Vibrational Symmetry Breaking in Self-Assembled Monolayers with Ultrahigh Vacuum Tip-Enhanced Raman Spectroscopy.

Ultrahigh vacuum tip-enhanced Raman spectroscopy (UHV-TERS) combines the atomic-scale imaging capability of scanning probe microscopy with the single-molecule chemical sensitivity and structural specificity of surface-enhanced Raman spectroscopy. Here, we use these techniques in combination with theory to reveal insights into the influence of intermolecular interactions on the vibrational spectra of a N-N'-bis(2,6-diisopropylphenyl)-perylene-3,4:9,10-bis(dicarboximide) (PDI) self-assembled monolayer adsorbed on single-crystal Ag substrates at room temperature. In particular, we have revealed the lifting of a vibrational degeneracy of a mode of PDI on Ag(111) and Ag(100) surfaces, with the most strongly perturbed mode being that associated with the largest vibrational amplitude on the periphery of the molecule. This work demonstrates that UHV-TERS enables direct measurement of molecule-molecule interaction at nanoscale. We anticipate that this information will advance the fundamental understanding of the most important effect of intermolecular interactions on the vibrational modes of surface-bound molecules.

Hidden role of intermolecular proton transfer in the anomalously diffuse vibrational spectrum of a trapped hydronium ion.

We report the vibrational spectra of the hydronium and methyl-ammonium ions captured in the C3v binding pocket of the 18-crown-6 ether ionophore. Although the NH stretching bands of the CH3NH3+ ion are consistent with harmonic expectations, the OH stretching bands of H3O+ are surprisingly broad, appearing as a diffuse background absorption with little intensity modulation over 800 cm-1 with an onset ∼400 cm-1 below the harmonic prediction. This structure persists even when only a single OH group is present in the HD2O+ isotopologue, while the OD stretching region displays a regular progression involving a soft mode at about 85 cm-1 These results are rationalized in a vibrationally adiabatic (VA) model in which the motion of the H3O+ ion in the crown pocket is strongly coupled with its OH stretches. In this picture, H3O+ resides in the center of the crown in the vibrational zero-point level, while the minima in the VA potentials associated with the excited OH vibrational states are shifted away from the symmetrical configuration displayed by the ground state. Infrared excitation between these strongly H/D isotope-dependent VA potentials then accounts for most of the broadening in the OH stretching manifold. Specifically, low-frequency motions involving concerted motions of the crown scaffold and the H3O+ ion are driven by a Franck-Condon-like mechanism. In essence, vibrational spectroscopy of these systems can be viewed from the perspective of photochemical interconversion between transient, isomeric forms of the complexes corresponding to the initial stage of intermolecular proton transfer.

Bisboronic Acids for Selective, Physiologically Relevant Direct Glucose Sensing with Surface-Enhanced Raman Spectroscopy.

This paper demonstrates the direct sensing of glucose at physiologically relevant concentrations with surface-enhanced Raman spectroscopy (SERS) on gold film-over-nanosphere (AuFON) substrates functionalized with bisboronic acid receptors. The combination of selectivity in the bisboronic acid receptor and spectral resolution in the SERS data allow the sensors to resolve glucose in high backgrounds of fructose and, in combination with multivariate statistical analysis, detect glucose accurately in the 1-10 mM range. Computational modeling supports assignments of the normal modes and vibrational frequencies for the monoboronic acid base of our bisboronic acids, glucose and fructose. These results are promising for the use of bisboronic acids as receptors in SERS-based in vivo glucose monitoring sensors.

Nanoscale Chemical Imaging of a Dynamic Molecular Phase Boundary with Ultrahigh Vacuum Tip-Enhanced Raman Spectroscopy.

Nanoscale chemical imaging of a dynamic molecular phase boundary has broad implications for a range of problems in catalysis, surface science, and molecular electronics. While scanning probe microscopy (SPM) is commonly used to study molecular phase boundaries, its information content can be severely compromised by surface diffusion, irregular packing, or three-dimensional adsorbate geometry. Here, we demonstrate the simultaneous chemical and structural analysis of N-N'-bis(2,6-diisopropylphenyl)-1,7-(4'-t-butylphenoxy)perylene-3,4:9,10-bis(dicarboximide) (PPDI) molecules by UHV tip-enhanced Raman spectroscopy. Both condensed and diffusing domains of PPDI coexist on Ag(100) at room temperature. Through comparison with time-dependent density functional theory simulations, we unravel the orientation of PPDI molecules at the dynamic molecular domain boundary with unprecedented ∼4 nm spatial resolution.

Atomistic simulations of CO2 and N2 within cage-type silica zeolites.

The behavior of CO(2) and N(2), both as single components and as binary mixtures, in two cage-type silica zeolites was studied using atomistic simulations. The zeolites considered, ITQ-3 and paradigm cage-type zeolite ZK4 (the all-silica analog of LTA), were chosen so that the principles illustrated can be generalized to other adsorbent/adsorbate systems with similar topology and types of interactions. N(2) was chosen both because of the potential uses of N(2)/CO(2) separations and because it differs from CO(2) most significantly in the magnitude of its Coulombic interactions with zeolites. Despite similarities between N(2) and CO(2) diffusion in other materials, we show here that the diffusion of CO(2) within cage-type zeolites is dominated by an energy barrier to diffusion located at the entrance to the narrow channels connecting larger cages. This barrier originates in Coulombic interactions between zeolites and CO(2)'s quadrupole and results in well-defined orientations for the diffusing molecules. Furthermore, CO(2)'s favorable electrostatic interactions with the zeolite framework result in preferential binding in the windows between cages. N(2)'s behavior, in contrast, is more consistent with that of molecules previously studied. Our analysis suggests that CO(2)'s behavior might be common for adsorbates with quadrupoles that interact strongly with a material that has narrow windows between cages.