Terahertz vibrational modes of the rigid crystal phase of succinonitrile

Daniel V. Nickel, Sean P. Delaney, Hongtao Bian, Junrong Zheng, Timothy Michael Korter, Daniel M. Mittleman

Research output: Contribution to journalArticle

20 Citations (Scopus)

Abstract

Succinonitrile (N≡C-CH2-CH2-C≡N), an orientationally disordered molecular plastic crystal at room temperature, exhibits rich phase behavior including a solid-solid phase transition at 238 K. In cooling through this phase transition, the high-temperature rotational disorder of the plastic crystal phase is frozen out, forming a rigid crystal that is both spatially and orientationally ordered. Using temperature-dependent terahertz time-domain spectroscopy, we characterize the vibrational modes of this low-temperature crystalline phase for frequencies from 0.3 to 2.7 THz and temperatures ranging from 20 to 220 K. Vibrational modes are observed at 1.122 and 2.33 THz at 90 K. These modes are assigned by solid-state density functional theory simulations, corresponding respectively to the translation and rotation of the molecules along and about their crystallographic c-axis. In addition, we observe a suppression of the phonon modes as the concentration of dopants, in this case a lithium salt (LiTFSI), increases, indicating the importance of doping-induced disorder in these ionic conductors.

Original languageEnglish (US)
Pages (from-to)2442-2446
Number of pages5
JournalJournal of Physical Chemistry A
Volume118
Issue number13
DOIs
StatePublished - Apr 3 2014

Fingerprint

succinonitrile
vibration mode
Crystals
plastics
disorders
crystals
Temperature
Phase transitions
Doping (additives)
solid phases
Plastics
conductors
lithium
retarding
density functional theory
salts
solid state
cooling
Phase behavior
Lithium

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Nickel, D. V., Delaney, S. P., Bian, H., Zheng, J., Korter, T. M., & Mittleman, D. M. (2014). Terahertz vibrational modes of the rigid crystal phase of succinonitrile. Journal of Physical Chemistry A, 118(13), 2442-2446. https://doi.org/10.1021/jp411865n

Terahertz vibrational modes of the rigid crystal phase of succinonitrile. / Nickel, Daniel V.; Delaney, Sean P.; Bian, Hongtao; Zheng, Junrong; Korter, Timothy Michael; Mittleman, Daniel M.

In: Journal of Physical Chemistry A, Vol. 118, No. 13, 03.04.2014, p. 2442-2446.

Research output: Contribution to journalArticle

Nickel, DV, Delaney, SP, Bian, H, Zheng, J, Korter, TM & Mittleman, DM 2014, 'Terahertz vibrational modes of the rigid crystal phase of succinonitrile', Journal of Physical Chemistry A, vol. 118, no. 13, pp. 2442-2446. https://doi.org/10.1021/jp411865n
Nickel, Daniel V. ; Delaney, Sean P. ; Bian, Hongtao ; Zheng, Junrong ; Korter, Timothy Michael ; Mittleman, Daniel M. / Terahertz vibrational modes of the rigid crystal phase of succinonitrile. In: Journal of Physical Chemistry A. 2014 ; Vol. 118, No. 13. pp. 2442-2446.
@article{cae75c75c1944ff884111b4b1e4947a4,
title = "Terahertz vibrational modes of the rigid crystal phase of succinonitrile",
abstract = "Succinonitrile (N≡C-CH2-CH2-C≡N), an orientationally disordered molecular plastic crystal at room temperature, exhibits rich phase behavior including a solid-solid phase transition at 238 K. In cooling through this phase transition, the high-temperature rotational disorder of the plastic crystal phase is frozen out, forming a rigid crystal that is both spatially and orientationally ordered. Using temperature-dependent terahertz time-domain spectroscopy, we characterize the vibrational modes of this low-temperature crystalline phase for frequencies from 0.3 to 2.7 THz and temperatures ranging from 20 to 220 K. Vibrational modes are observed at 1.122 and 2.33 THz at 90 K. These modes are assigned by solid-state density functional theory simulations, corresponding respectively to the translation and rotation of the molecules along and about their crystallographic c-axis. In addition, we observe a suppression of the phonon modes as the concentration of dopants, in this case a lithium salt (LiTFSI), increases, indicating the importance of doping-induced disorder in these ionic conductors.",
author = "Nickel, {Daniel V.} and Delaney, {Sean P.} and Hongtao Bian and Junrong Zheng and Korter, {Timothy Michael} and Mittleman, {Daniel M.}",
year = "2014",
month = "4",
day = "3",
doi = "10.1021/jp411865n",
language = "English (US)",
volume = "118",
pages = "2442--2446",
journal = "Journal of Physical Chemistry A",
issn = "1089-5639",
publisher = "American Chemical Society",
number = "13",

}

TY - JOUR

T1 - Terahertz vibrational modes of the rigid crystal phase of succinonitrile

AU - Nickel, Daniel V.

AU - Delaney, Sean P.

AU - Bian, Hongtao

AU - Zheng, Junrong

AU - Korter, Timothy Michael

AU - Mittleman, Daniel M.

PY - 2014/4/3

Y1 - 2014/4/3

N2 - Succinonitrile (N≡C-CH2-CH2-C≡N), an orientationally disordered molecular plastic crystal at room temperature, exhibits rich phase behavior including a solid-solid phase transition at 238 K. In cooling through this phase transition, the high-temperature rotational disorder of the plastic crystal phase is frozen out, forming a rigid crystal that is both spatially and orientationally ordered. Using temperature-dependent terahertz time-domain spectroscopy, we characterize the vibrational modes of this low-temperature crystalline phase for frequencies from 0.3 to 2.7 THz and temperatures ranging from 20 to 220 K. Vibrational modes are observed at 1.122 and 2.33 THz at 90 K. These modes are assigned by solid-state density functional theory simulations, corresponding respectively to the translation and rotation of the molecules along and about their crystallographic c-axis. In addition, we observe a suppression of the phonon modes as the concentration of dopants, in this case a lithium salt (LiTFSI), increases, indicating the importance of doping-induced disorder in these ionic conductors.

AB - Succinonitrile (N≡C-CH2-CH2-C≡N), an orientationally disordered molecular plastic crystal at room temperature, exhibits rich phase behavior including a solid-solid phase transition at 238 K. In cooling through this phase transition, the high-temperature rotational disorder of the plastic crystal phase is frozen out, forming a rigid crystal that is both spatially and orientationally ordered. Using temperature-dependent terahertz time-domain spectroscopy, we characterize the vibrational modes of this low-temperature crystalline phase for frequencies from 0.3 to 2.7 THz and temperatures ranging from 20 to 220 K. Vibrational modes are observed at 1.122 and 2.33 THz at 90 K. These modes are assigned by solid-state density functional theory simulations, corresponding respectively to the translation and rotation of the molecules along and about their crystallographic c-axis. In addition, we observe a suppression of the phonon modes as the concentration of dopants, in this case a lithium salt (LiTFSI), increases, indicating the importance of doping-induced disorder in these ionic conductors.

UR - http://www.scopus.com/inward/record.url?scp=84898077548&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84898077548&partnerID=8YFLogxK

U2 - 10.1021/jp411865n

DO - 10.1021/jp411865n

M3 - Article

AN - SCOPUS:84898077548

VL - 118

SP - 2442

EP - 2446

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

SN - 1089-5639

IS - 13

ER -