| 62 |
|
with a terminal nitrile group aligned with the long axis of the |
| 63 |
|
molecule. Simulations of condensed-phase 5CB were carried out both |
| 64 |
|
with and without applied electric fields to provide an understanding |
| 65 |
< |
of the the Stark shift of the terminal nitrile group. A |
| 66 |
< |
field-induced isotropic-nematic phase transition was observed in the |
| 67 |
< |
simulations, and the effects of this transition on the distribution |
| 68 |
< |
of nitrile frequencies were computed. Classical bond displacement |
| 69 |
< |
correlation functions exhibit a $\sim 40 \mathrm{~cm}^{-1}$ red |
| 70 |
< |
shift of a portion of the main nitrile peak, and this shift was |
| 71 |
< |
observed only when the fields were large enough to induce |
| 72 |
< |
orientational ordering of the bulk phase. Our simulations appear to |
| 73 |
< |
indicate that phase-induced changes to the local surroundings are a |
| 74 |
< |
larger contribution to the change in the nitrile spectrum than |
| 75 |
< |
direct field contributions. |
| 65 |
> |
of the Stark shift of the terminal nitrile group. A field-induced |
| 66 |
> |
isotropic-nematic phase transition was observed in the simulations, |
| 67 |
> |
and the effects of this transition on the distribution of nitrile |
| 68 |
> |
frequencies were computed. Classical bond displacement correlation |
| 69 |
> |
functions exhibit a $\sim 40 \mathrm{~cm}^{-1}$ red shift of a |
| 70 |
> |
portion of the main nitrile peak, and this shift was observed only |
| 71 |
> |
when the fields were large enough to induce orientational ordering |
| 72 |
> |
of the bulk phase. Joint spatial-angular distribution functions |
| 73 |
> |
indicate that phase-induced anti-caging of the nitrile bond is |
| 74 |
> |
contributing to the change in the nitrile spectrum. |
| 75 |
|
\end{abstract} |
| 76 |
|
|
| 77 |
|
\newpage |
