A study into the effect of subtle structural details and disorder on the terahertz spectrum of crystalline benzoic acid

被引：72

作者：

Li, Ruoyu ^{[1
]}

Zeitler, J. Axel ^{[1
]}

Tomerini, Daniele ^{[2
]}

Parrott, Edward P. J. ^{[1
,3
]}

Gladden, Lynn F. ^{[1
]}

Day, Graeme M. ^{[2
]}

机构：

[1] Univ Cambridge, Dept Chem Engn & Biotechnol, Cambridge CB2 3RA, England

[2] Univ Cambridge, Dept Chem, Cambridge CB2 1EW, England

[3] Univ Cambridge, Cavendish Lab, Cambridge CB3 0HE, England

来源：

PHYSICAL CHEMISTRY CHEMICAL PHYSICS | 2010年 / 12卷 / 20期

基金：

英国工程与自然科学研究理事会;

关键词：

TIME-DOMAIN SPECTROSCOPY; RIGID ORGANIC-MOLECULES; PULSED SPECTROSCOPY; TEMPERATURE-DEPENDENCE; NEUTRON-DIFFRACTION; VIBRATIONAL-MODES; PROTON-TRANSFER; PHONON FREQUENCIES; CARBOXYLIC-ACIDS; LATTICE-DYNAMICS;

D O I：

10.1039/b926536h

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The phonon modes of crystalline benzoic acid have been investigated using terahertz time-domain spectroscopy, rigid molecule atom-atom model potential and plane-wave density functional theory lattice dynamics calculations. The simulation results show good agreement with the measured terahertz spectra and an assignment of the terahertz absorption features of benzoic acid is made with the help of both computational methods. Focussing on the strongest interactions in the crystal, we describe each vibration in terms of distortions of the benzoic acid hydrogen bonded dimers that are present in the crystal structure. The terahertz spectrum is also shown to be highly sensitive to the location of the carboxylic acid hydrogen atoms in the cyclic hydrogen-bonded dimers and we have systematically explored the influence of the observed disorder in the hydrogen atom positions on the lattice dynamics.

引用

页码：5329 / 5340

页数：12

共 47 条

[1] Solid-state modeling of the terahertz spectrum of the high explosive HMX [J].

Allis, DG ;

Prokhorova, DA ;

Korter, TM .

JOURNAL OF PHYSICAL CHEMISTRY A, 2006, 110 (05) :1951-1959

[2] Dimer or catemer? Low-energy crystal packings for small carboxylic acids [J].

Beyer, T ;

Price, SL .

JOURNAL OF PHYSICAL CHEMISTRY B, 2000, 104 (12) :2647-2655

[3] B3LYP augmented with an empirical dispersion term (B3LYP-D*) as applied to molecular crystals [J].

Civalleri, Bartolomeo ;

Zicovich-Wilson, Claudio M. ;

Valenzano, Loredana ;

Ugliengo, Piero .

CRYSTENGCOMM, 2008, 10 (04) :405-410

[4] First principles methods using CASTEP [J].

Clark, SJ ;

Segall, MD ;

Pickard, CJ ;

Hasnip, PJ ;

Probert, MJ ;

Refson, K ;

Payne, MC .

ZEITSCHRIFT FUR KRISTALLOGRAPHIE, 2005, 220 (5-6) :567-570

[5] NONBONDED POTENTIAL FUNCTION MODELS FOR CRYSTALLINE OXOHYDROCARBONS [J].

COX, SR ;

HSU, LY ;

WILLIAMS, DE .

ACTA CRYSTALLOGRAPHICA SECTION A, 1981, 37 (MAY) :293-301

[6] Understanding the influence of polymorphism on phonon spectra: Lattice dynamics calculations and terahertz spectroscopy of carbamazepine [J].

Day, GM ;

Zeitler, JA ;

Jones, W ;

Rades, T ;

Taday, PF .

JOURNAL OF PHYSICAL CHEMISTRY B, 2006, 110 (01) :447-456

[7] Atomistic calculations of phonon frequencies and thermodynamic quantities for crystals of rigid organic molecules [J].

Day, GM ;

Price, SL ;

Leslie, M .

JOURNAL OF PHYSICAL CHEMISTRY B, 2003, 107 (39) :10919-10933

[8] THE CRYSTAL-STRUCTURE OF BENZOIC-ACID - A REDETERMINATION WITH X-RAYS AT ROOM-TEMPERATURE - A SUMMARY OF NEUTRON-DIFFRACTION WORK AT TEMPERATURES DOWN TO 5K [J].

FELD, R ;

LEHMANN, MS ;

MUIR, KW ;

SPEAKMAN, JC .

ZEITSCHRIFT FUR KRISTALLOGRAPHIE, 1981, 157 (3-4) :215-231

[9] Fluorescence-dip IR spectra of jet-cooled benzoic acid dimer in its ground and first excited singlet states [J].

Florio, GM ;

Sibert, EL ;

Zwier, TS .

FARADAY DISCUSSIONS, 2001, 118 :315-330

[10]

Frisch M. J., 2004, GAUSSIAN 03

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