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\title{Nitrile vibrations as reporters of field-induced phase |
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transitions in liquid crystals} |
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\author{James M. Marr} |
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\author{J. Daniel Gezelter} |
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\email{gezelter@nd.edu} |
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\affiliation[University of Notre Dame]{251 Nieuwland Science Hall\\ |
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Department of Chemistry and Biochemistry\\ |
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University of Notre Dame\\ |
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Notre Dame, Indiana 46556} |
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\date{\today} |
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\begin{document} |
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\maketitle |
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\begin{doublespace} |
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\begin{abstract} |
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4-Cyano-4'-pentylbiphenyl (5CB) is a liquid-crystal-forming compound |
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with a terminal nitrile group aligned with the long axis of the |
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molecule. Simulations of condensed-phase 5CB were carried out both |
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with and without applied electric fields to provide an understanding |
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of the various contributions to the Stark shift of the terminal |
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nitrile group. A field-induced isotropic-nematic phase transition |
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was observed in the simulations, and the effects of this transition |
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on the distribution of nitrile frequencies were computed. Classical |
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bond displacement correlation functions exhibited a ($\sim 40 |
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\mathrm{cm}^{-1}$ red shift of a fraction of the main nitrile peak, |
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and this shift was observed only when the fields were large enough |
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to induce orientational ordering of the bulk phase. Our simulations |
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appear to indicate that phase-induced changes to the local |
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surroundings are a larger contribution to the change in the nitrile |
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spectrum than the direct field contribution. |
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\end{abstract} |
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\newpage |
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\section{Introduction} |
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The Stark shift of nitrile groups in response to applied electric |
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fields have been used extensively in biology for probing the internal |
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fields of structures like proteins and DNA. Integration of these |
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probes into different materials is also important for studying local |
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structure in confined fluids. This work centers on the vibrational |
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response of the terminal nitrile group in 4-Cyano-4'-pentylbiphenyl |
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(5CB), a liquid crystalline molecule with an isotropic to nematic |
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phase transition that can be triggered by the application of an |
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external field. |
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|
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The fundamental characteristic of liquid crystal mesophases is that |
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they maintain some degree of orientational order while translational |
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order is limited or absent. This orientational order produces a |
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complex direction-dependent response to external perturbations like |
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electric fields and mechanical distortions. The anisotropy of the |
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macroscopic phases originates in the anisotropy of the constituent |
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molecules, which typically have highly non-spherical structures with a |
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significant degree of internal rigidity. In nematic phases, rod-like |
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molecules are orientationally ordered with isotropic distributions of |
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molecular centers of mass, while in smectic phases, the molecules |
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arrange themselves into layers with their long (symmetry) axis normal |
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($S_{A}$) or tilted ($S_{C}$) with respect to the layer planes. |
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The behavior of the $S_{A}$ phase can be partially explained with |
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models mainly based on geometric factors and van der Waals |
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interactions. However, these simple models are insufficient to |
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describe liquid crystal phases which exhibit more complex polymorphic |
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nature. X-ray diffraction studies have shown that the ratio between |
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lamellar spacing ($s$) and molecular length ($l$) can take on a wide |
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range of values.\cite{Gray:1984hc,Leadbetter:1976vf,Hardouin:1980yq} |
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Typical $S_{A}$ phases have $s/l$ ratios on the order of $0.8$, while |
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for some compounds, e.g. the 4-alkyl-4'-cyanobiphenyls, the $s/l$ |
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ratio is on the order of $1.4$. Molecules which form $S_{A}$ phases |
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can exhibit a wide variety of subphases like monolayers ($S_{A1}$), |
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uniform bilayers ($S_{A2}$), partial bilayers ($S_{\tilde A}$) as well |
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as interdigitated bilayers ($S_{A_{d}}$), and often have a terminal |
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cyano or nitro group. In particular, lyotropic liquid crystals (those |
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exhibiting liquid crystal phase transition as a function of water |
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concentration), often have polar head groups or zwitterionic charge |
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separated groups that result in strong dipolar |
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interactions.\cite{Collings97} Because of their versatile polymorphic |
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nature, polar liquid crystalline materials have important |
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technological applications in addition to their immense relevance to |
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biological systems.\cite{Collings97} |
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Experimental studies by Levelut {\it et al.}~\cite{Levelut:1981eu} |
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revealed that terminal cyano or nitro groups usually induce permanent |
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longitudinal dipole moments on the molecules. Liquid crystalline |
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materials with dipole moments located at the ends of the molecules |
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have important applications in display technologies in addition to |
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their relevance in biological systems.\cite{LCapp} |
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Many of the technological applications of the lyotropic mesogens |
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manipulate the orientation and structuring of the liquid crystal |
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through application of external electric fields.\cite{?} |
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Macroscopically, this restructuring is visible in the interactions the |
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bulk phase has with scattered or transmitted light.\cite{?} |
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4-Cyano-4'-pentylbiphenyl (5CB), has been a model for field-induced |
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phase changes due to the well-studied electric field |
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response,\cite{Hatta:1991ee} and the fact that it has a set of phase |
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transitions near room temperature.\cite{Gray:1973ca} The have a solid |
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to nematic phase transition at 18 C and a nematic to isotropic |
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transition at 35 C.\cite{Gray:1973ca} Recently there has been renewed |
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interest in 5CB in nanodroplets to understand defect sites and |
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nanoparticle structuring.\cite{PhysRevLett.111.227801} |
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Nitrile groups can serve as very precise electric field reporters via |
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their distinctive Raman and IR signatures.\cite{Boxer:2009xw} The |
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triple bond between the nitrogen and the carbon atom is very sensitive |
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to local field changes and is observed to have a direct impact on the |
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peak position within the spectrum. The Stark shift in the spectrum |
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can be quantified and mapped into a field value that is impinging upon |
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the nitrile bond. This has been used extensively in biological systems |
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like proteins and enzymes.\cite{Tucker:2004qq,Webb:2008kn} |
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To date, the nitrile electric field response of |
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4-Cyano-4'-n-alkylbiphenyl liquid crystals has not been investigated. |
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While macroscopic electric fields applied across macro electrodes show |
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the phase change of the molecule as a function of electric |
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field,\cite{Lim:2006xq} the effect of a nanoscopic field application |
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has not been probed. These previous studies have shown the nitrile |
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group serves as an excellent indicator of the molecular orientation |
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within the field applied. Lee {\it et al.}~showed the 180 degree |
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change in field direction could be probed with the nitrile peak |
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intensity as it decreased and increased with molecule alignment in the |
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field.\cite{Lee:2006qd,Leyte:97} |
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While these macroscopic fields worked well at showing the bulk |
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response, the atomic scale response has not been studied. With the |
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advent of nano-electrodes and coupling them with atomic force |
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microscopy, control of electric fields applied across nanometer |
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distances is now possible\cite{citation1}. This application of |
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nanometer length is interesting in the case of a nitrile group on the |
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molecule. While macroscopic fields are insufficient to cause a Stark |
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effect, small fields across nanometer-sized gaps are of sufficient |
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strength. If one were to assume a gap of 5 nm between a lower |
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electrode having a nanoelectrode placed near it via an atomic force |
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microscope, a field of 1 V applied across the electrodes would |
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translate into a field of 2x10\textsuperscript{8} $\frac{V}{M}$. This |
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field is theoretically strong enough to cause a phase change from |
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isotropic to nematic, as well as Stark tuning of the nitrile |
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bond. This should be readily visible experimentally through Raman or |
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IR spectroscopy. |
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In the rest of this paper, we outline a series of classical molecular |
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dynamics simulations of 5CB that were done in the presence of static |
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electric fields. These simulations were then coupled with both {\it ab |
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intio} calculations of CN-deformations and classical correlation |
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functions to predict spectral shifts. These predictions should be |
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easily varifiable with scanning electrochemical microscopy |
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experiments. |
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\section{Computational Details} |
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The force field used for 5CB was taken from Guo {\it et |
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al.}\cite{Zhang:2011hh} However, for most of the simulations, each |
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of the phenyl rings was treated as a rigid body to allow for larger |
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time steps and very long simulation times. The geometries of the |
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rigid bodies were taken from equilibrium bond distances and angles. |
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Although the phenyl rings were held rigid, bonds, bends, torsions and |
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inversion centers included in these bodies (but with connectivity to |
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the rest of the molecule) were still included in the potential and |
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force calculations. |
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Periodic simulations cells contained 270 molecules and were locked at |
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experimental densities. Electrostatic interactions were computed |
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using damped shifted force (DSF) electrostatics.\cite{Fennell:2006zl} |
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The molecules were equilibrated for 1~ns at a temperature of 300K. |
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Simulations with applied fields were carried out in the microcanonical |
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(NVE) ensemble with an energy corresponding to the average energy from |
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the canonical (NVT) equilibration runs. Typical applied-field runs |
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were more than 60ns in length. |
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Static electric fields with magnitudes similar to what would be |
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available in an experimental setup were applied to the different |
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simulations. With an assumed electrode seperation of 5 nm and an |
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electrostatic potential that is limited by the voltage required to |
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split water (1.23V), the maximum realistic field that could be applied |
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is $\sim 0.024 V / \AA$. Three field environments were investigated: |
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(1) no field applied, (2) $0.01 V / \AA$ (0.5 V), and (3) $0.024 V / |
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\AA$ (1.2 V). Each field was applied along the $z$-axis of the |
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simulation cell. For simplicity, these field strengths will be |
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referred to as zero, partial, and full field. |
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After the systems had come to equilibrium under the applied fields, |
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additional simulations were carried out with a flexible (harmonic) |
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nitrile bond with an equilibrium bond distance of XXX \AA and a force |
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constant of XXX kcal / mol $\AA^2$, corresponding to a vibrational |
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frequency of YYYY $\mathrm{cm}^{-1}$. The flexible nitrile moiety |
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required simualtion time steps of 1fs, so the additional flexibility |
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was introducuced only after the rigid systems had come to equilibrium |
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under the applied fields. Whenever time correlation functions were |
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computed from the flexible simulations, statistically-independent |
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configurations were sampled from the last ns of the induced-field |
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runs. These configurations were then equilibrated with the flexible |
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nitrile moiety for 100 ps, and time correlation functions were |
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computed using data sampled from an additional 200 ps of run time |
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carried out in the microcanonical ensemble. |
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\section{Field-induced Nematic Ordering} |
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In order to characterize the orientational ordering of the system, the |
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primary quantity of interest is the nematic (orientational) order |
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parameter. This was determined using the tensor |
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\begin{equation} |
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Q_{\alpha \beta} = \frac{1}{2N} \sum_{i=1}^{N} \left(3 \hat{e}_{i |
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\alpha} \hat{e}_{i \beta} - \delta_{\alpha \beta} \right) |
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\end{equation} |
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where $\alpha, \beta = x, y, z$, and $\hat{e}_i$ is the molecular |
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end-to-end unit vector for molecule $i$. The nematic order parameter |
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$S$ is the largest eigenvalue of $Q_{\alpha \beta}$, and the |
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corresponding eigenvector defines the director axis for the phase. |
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$S$ takes on values close to 1 in highly ordered (smectic A) phases, |
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but falls to zero for isotropic fluids. In nematic phases, typical |
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values are close to 0.5. |
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In Figure \ref{fig:orderParameter}, the field-induced phase change can |
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be clearly seen over the course of a 60 ns equilibration run. All |
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three of the systems started in a random (isotropic) packing, with |
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order parameters near 0.2. Over the course 10 ns, the full field |
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causes an alignment of the molecules (due primarily to the interaction |
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of the nitrile group dipole with the electric field). Once this |
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system landed in the nematic-ordered state, it became stable for the |
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remaining 50 ns of simulation time. It is possible that the |
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partial-field simulation is meta-stable and given enough time, it |
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would eventually find a nematic-ordered phase, but the partial-field |
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simulation was stable as an isotropic phase for the full duration of a |
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60 ns simulation. |
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\begin{figure} |
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\includegraphics[trim = 5mm 10mm 3mm 10mm, clip, width=3.25in]{P2} |
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\caption{Ordering of each external field application over the course |
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of 60 ns with a sampling every 100 ps. Each trajectory was started |
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after equilibration with zero field applied.} |
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\label{fig:orderParameter} |
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\end{figure} |
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In figure \ref{fig:Cigars}, the field-induced isotropic-nematic |
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transition is represented using ellipsoids aligned along the long-axis |
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of each molecule. The vector between the nitrogen of the nitrile |
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group and the terminal tail atom is used to orient each |
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ellipsoid. Both the zero field and partial field simulations appear |
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isotropic, while the full field simulations has clearly been |
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orientationally ordered |
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\begin{figure} |
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\includegraphics[width=7in]{Elip_3} |
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\caption{Ellipsoid reprsentation of 5CB at three different |
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field strengths, Zero Field (Left), Partial Field (Middle), and Full |
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Field (Right) Each image was created by taking the final |
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snapshot of each 60 ns run} |
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\label{fig:Cigars} |
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\end{figure} |
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\section{Analysis} |
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|
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For quantum calculation of the nitrile bond frequency, Gaussian 09 was |
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used. A single 5CB molecule was selected for the center of the |
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cluster. For effects from molecules located near the chosen nitrile |
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group, parts of molecules nearest to the nitrile group were |
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included. For the body not including the tail, any atom within 6~\AA |
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of the midpoint of the nitrile group was included. For the tail |
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structure, the whole tail was included if a tail atom was within 4~\AA |
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of the midpoint. If the tail did not include any atoms from the ring |
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structure, it was considered a propane molecule and included as |
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such. Once the clusters were generated, input files were created that |
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stretched the nitrile bond along its axis from 0.87 to 1.52~\AA at |
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increments of 0.05~\AA. This generated 13 single point energies to be |
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calculated. The Gaussian files were run with B3LYP/6-311++G(d,p) with |
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no other keywords for the zero field simulation. Simulations with |
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fields applied included the keyword ''Field=Z+5'' to match the |
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external field applied in molecular dynamic runs. Once completed, the central nitrile bond frequency |
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was calculated with a Morse fit. Using this fit and the solved energy |
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levels for a Morse oscillator, the frequency was found. Each set of |
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frequencies were then convolved together with a lorezian lineshape |
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function over each value. The width value used was 1.5. For the zero |
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field spectrum, 67 frequencies were used and for the full field, 59 |
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frequencies were used. |
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Classical nitrile bond frequencies were found by replacing the rigid |
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cyanide bond with a flexible Morse oscillator bond |
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($r_0= 1.157437$ \AA , $D_0 = 212.95$ and |
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$\beta = 2.67566$) . Once replaced, the |
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systems were allowed to re-equilibrate in NVT for 100 ps. After |
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re-equilibration, the system was run in NVE for 20 ps with a snapshot |
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spacing of 1 fs. These snapshot were then used in bond correlation |
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calculation to find the decay structure of the bond in time using the |
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average bond displacement in time, |
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\begin{equation} |
328 |
|
|
C(t) = \langle \left(r(t) - r_0 \right) \cdot \left(r(0) - r_0 \right) \rangle |
329 |
|
|
\end{equation} |
330 |
|
|
% |
331 |
|
|
where $r_0$ is the equilibrium bond distance and $r(t)$ is the |
332 |
|
|
instantaneous bond displacement at time $t$. Once calculated, |
333 |
|
|
smoothing was applied by adding an exponential decay on top of the |
334 |
jmarr |
4023 |
decay with a $\tau$ of 6000. Further smoothing |
335 |
gezelter |
4007 |
was applied by padding 20,000 zeros on each side of the symmetric |
336 |
|
|
data. This was done five times by allowing the systems to run 1 ns |
337 |
|
|
with a rigid bond followed by an equilibrium run with the bond |
338 |
jmarr |
4023 |
switched back to a Morse oscillator and a short production run of 20 ps. |
339 |
gezelter |
4007 |
|
340 |
|
|
\section{Results} |
341 |
|
|
|
342 |
|
|
|
343 |
jmarr |
4017 |
|
344 |
jmarr |
4020 |
|
345 |
jmarr |
4017 |
This change in phase was followed by two courses of further |
346 |
jmarr |
4019 |
analysis. First was the replacement of the static nitrile bond with a |
347 |
jmarr |
4017 |
morse oscillator bond. This was then simulated for a period of time |
348 |
jmarr |
4022 |
and a classical spetrum was calculated. Second, ab intio calcualtions |
349 |
jmarr |
4023 |
were performed to investigate if the phase change caused any change |
350 |
|
|
spectrum through quantum effects. |
351 |
jmarr |
4017 |
|
352 |
jmarr |
4019 |
The classical nitrile spectrum can be seen in Figure 2. Most noticably |
353 |
|
|
is the position of the two peaks. Obviously the experimental peak |
354 |
|
|
position is near 2226 cm\textsuperscript{-1}. However, in this case |
355 |
|
|
the peak position is shifted to the blue at a position of 2375 |
356 |
|
|
cm\textsuperscript{-1}. This shift is due solely to the choice of |
357 |
jmarr |
4022 |
oscillator strength in the Morse oscillator parameters. While this |
358 |
jmarr |
4019 |
shift makes the two spectra differ, it does not affect the ability to |
359 |
jmarr |
4022 |
qualitatively compare peak changes to possible experimental changes. |
360 |
jmarr |
4019 |
With this important fact out of the way, differences between the two |
361 |
|
|
states are subtle but are very much present. The first and |
362 |
|
|
most notable is the apperance for a strong band near 2300 |
363 |
jmarr |
4020 |
cm\textsuperscript{-1}. |
364 |
jmarr |
4013 |
\begin{figure} |
365 |
|
|
\includegraphics[width=3.25in]{2Spectra} |
366 |
jmarr |
4017 |
\caption{The classically calculated nitrile bond spetrum for no |
367 |
|
|
external field application (black) and full external field |
368 |
|
|
application (red)} |
369 |
jmarr |
4013 |
\label{fig:twoSpectra} |
370 |
|
|
\end{figure} |
371 |
jmarr |
4020 |
|
372 |
jmarr |
4021 |
Before Gaussian silumations were carried out, it was attempt to apply |
373 |
jmarr |
4025 |
the method developed by Cho {\it et al.}~\cite{Oh:2008fk} This method involves the fitting |
374 |
jmarr |
4023 |
of multiple parameters to Gaussian calculated freuencies to find a |
375 |
|
|
correlation between the potential around the bond and the |
376 |
jmarr |
4025 |
frequency. This is very similar to work done by Skinner {\it et al.}~with |
377 |
jmarr |
4023 |
water models like SPC/E. The general method is to find the shift in |
378 |
|
|
the peak position through, |
379 |
jmarr |
4021 |
\begin{equation} |
380 |
jmarr |
4023 |
\delta\tilde{\nu} =\sum^{n}_{a=1} l_{a}\phi^{water}_{a} |
381 |
|
|
\end{equation} |
382 |
|
|
where $l_{a}$ are the fitting parameters and $\phi^{water}_{a}$ is the |
383 |
|
|
potential from the surrounding water cluster. This $\phi^{water}_{a}$ |
384 |
|
|
takes the form, |
385 |
|
|
\begin{equation} |
386 |
jmarr |
4021 |
\phi_{a} = \frac{1}{4\pi \epsilon_{0}} \sum_{m} \sum_{j} |
387 |
|
|
\frac{C^{H_{2}O}_{j \left(m \right) }}{r_{aj \left(m\right)}} |
388 |
|
|
\end{equation} |
389 |
jmarr |
4023 |
where $C^{H_{2}O}_{j \left(m \right) }$ indicates the partial charge |
390 |
|
|
on the $j$th site of the $m$th water molecule and $r_{aj \left(m\right)}$ |
391 |
|
|
is the distance between the site $a$ of the nitrile molecule and the $j$th |
392 |
|
|
site of the $m$th water molecule. However, since these simulations |
393 |
jmarr |
4024 |
are done under the presence of external fields and in the |
394 |
|
|
absence of water, the equations need a correction factor for the shift |
395 |
|
|
caused by the external field. The equation is also reworked to use |
396 |
|
|
electric field site data instead of partial charges from surrounding |
397 |
|
|
atoms. So by modifing the original |
398 |
jmarr |
4023 |
$\phi^{water}_{a}$ to $\phi^{5CB}_{a}$ we get, |
399 |
|
|
\begin{equation} |
400 |
|
|
\phi^{5CB}_{a} = \frac{1}{4\pi \epsilon_{0}} \left( \vec{E}\bullet |
401 |
|
|
\left(\vec{r}_{a}-\vec{r}_{CN}\right) \right) + \phi^{5CB}_{0} |
402 |
|
|
\end{equation} |
403 |
|
|
where $\vec{E}$ is the electric field at each atom, $\left( \vec{r}_{a} - |
404 |
|
|
\vec{r}_{CN} \right)$ is the vector between the nitrile bond and the |
405 |
|
|
cooridinates described by Cho around the bond and $\phi^{5CB}_{0}$ is |
406 |
|
|
the correction factor for the system of parameters. After these |
407 |
|
|
changes, the correction factor was found for multiple values of an |
408 |
|
|
external field being applied. However, the factor was no linear and |
409 |
|
|
was overly large due to the fitting parameters being so small. |
410 |
jmarr |
4020 |
|
411 |
jmarr |
4023 |
Due to this, Gaussian calculations were performed in lieu of this |
412 |
|
|
method. A set of snapshots for the zero and full field simualtions, |
413 |
|
|
they were first investigated for any dependence on the local, with |
414 |
|
|
external field included, electric field. This was to see if a linear |
415 |
|
|
or non-linear relationship between the two could be utilized for |
416 |
|
|
generating spectra. This was done in part because of previous studies |
417 |
|
|
showing the frequency dependence of nitrile bonds to the electric |
418 |
|
|
fields generated locally between solvating water. It was seen that |
419 |
|
|
little to no dependence could be directly shown. This data is not |
420 |
|
|
shown. |
421 |
|
|
|
422 |
jmarr |
4020 |
Since no explicit dependence was observed between the calculated |
423 |
|
|
frequency and the electric field, it was not a viable route for the |
424 |
|
|
calculation of a nitrile spectrum. Instead, the frequencies were taken |
425 |
jmarr |
4024 |
and convolved together with a lorentzian line shape applied around the |
426 |
|
|
frequency value. These spectra are seen below in Figure |
427 |
jmarr |
4020 |
4. While the spectrum without a field is lower in intensity and is |
428 |
jmarr |
4024 |
almost bimodel in distrobution, the external field spectrum is much |
429 |
jmarr |
4023 |
more unimodel. This tighter clustering has the affect of increasing the |
430 |
jmarr |
4020 |
intensity around 2226 cm\textsuperscript{-1} where the peak is |
431 |
jmarr |
4023 |
centered. The external field also has fewer frequencies of higher |
432 |
|
|
energy in the spectrum. Unlike the the zero field, where some frequencies |
433 |
|
|
reach as high as 2280 cm\textsuperscript{-1}. |
434 |
jmarr |
4013 |
\begin{figure} |
435 |
jmarr |
4018 |
\includegraphics[width=3.25in]{Convolved} |
436 |
jmarr |
4020 |
\caption{Lorentzian convolved Gaussian frequencies of the zero field |
437 |
|
|
system (black) and the full field system (red)} |
438 |
jmarr |
4018 |
\label{fig:Con} |
439 |
|
|
\end{figure} |
440 |
gezelter |
4007 |
\section{Discussion} |
441 |
jmarr |
4024 |
Interestingly, the field that is needed to switch the phase of 5CB |
442 |
|
|
macroscopically is larger than 1 V. However, in this case, only a |
443 |
|
|
voltage of 1.2 V was need to induce a phase change. This is impart due |
444 |
|
|
to the short distance of 5 nm the field is being applied across. At such a small |
445 |
|
|
distance, the field is much larger than the macroscopic and thus |
446 |
|
|
easily induces a field dependent phase change. However, this field |
447 |
|
|
will not cause a breakdown of the 5CB since electrochemistry studies |
448 |
|
|
have shown that it can be used in the presence of fields as high as |
449 |
|
|
500 V macroscopically. This large of a field near the surface of the |
450 |
|
|
elctrode would cause breakdown of 5CB if it could happen. |
451 |
|
|
|
452 |
jmarr |
4020 |
The absence of any electric field dependency of the freuquency with |
453 |
jmarr |
4025 |
the Gaussian simulations is interesting. A large base of research has been |
454 |
jmarr |
4024 |
built upon the known tuning of the nitrile bond as the local field |
455 |
|
|
changes. This difference may be due to the absence of water or a |
456 |
|
|
molecule that induces a large internal field. Liquid water is known to have a very high internal field which |
457 |
jmarr |
4020 |
is much larger than the internal fields of neat 5CB. Even though the |
458 |
jmarr |
4024 |
application of Gaussian simulations followed by mapping it to |
459 |
jmarr |
4020 |
some classical parameter is easy and straight forward, this system |
460 |
|
|
illistrates how that 'go to' method can break down. |
461 |
gezelter |
4007 |
|
462 |
jmarr |
4020 |
While this makes the application of nitrile Stark effects in |
463 |
jmarr |
4024 |
simulations without water harder, these data show |
464 |
jmarr |
4021 |
that it is not a deal breaker. The classically calculated nitrile |
465 |
|
|
spectrum shows changes in the spectra that will be easily seen through |
466 |
|
|
experimental routes. It indicates a shifted peak lower in energy |
467 |
jmarr |
4024 |
should arise. This peak is a few wavenumbers from the leading edge of |
468 |
|
|
the larger peak and almost 75 wavenumbers from the center. This |
469 |
|
|
seperation between the two peaks means experimental results will show |
470 |
|
|
an easily resolved peak. |
471 |
jmarr |
4021 |
|
472 |
jmarr |
4024 |
The Gaussian derived spectra do indicate an applied field |
473 |
jmarr |
4023 |
and subsiquent phase change does cause a narrowing of freuency |
474 |
jmarr |
4025 |
distrobution. With narrowing, it would indicate an increased |
475 |
|
|
homogeneous distrobution of the local field near the nitrile. |
476 |
gezelter |
4007 |
\section{Conclusions} |
477 |
jmarr |
4024 |
Field dependent changes |
478 |
gezelter |
4007 |
\newpage |
479 |
|
|
|
480 |
|
|
\bibliography{5CB} |
481 |
|
|
|
482 |
|
|
\end{doublespace} |
483 |
|
|
\end{document} |