Simulating infrared spectra and hydrogen bonding in cellulose Iβ at elevated temperatures

被引:102
作者
Agarwal, Vishal [1 ]
Huber, George W. [1 ]
Conner, W. Curtis, Jr. [1 ]
Auerbach, Scott M. [1 ,2 ]
机构
[1] Univ Massachusetts, Dept Chem Engn, Amherst, MA 01003 USA
[2] Univ Massachusetts, Dept Chem, Amherst, MA 01003 USA
基金
美国国家科学基金会;
关键词
TIME-CORRELATION FUNCTIONS; RADIANT FLASH PYROLYSIS; MOLECULAR-DYNAMICS; BIOMASS PYROLYSIS; VIBRATIONAL-SPECTRA; THERMAL-EXPANSION; NATIVE CELLULOSE; CELL-WALL; X-RAY; CRYSTALLINE POLYSACCHARIDES;
D O I
10.1063/1.3646306
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
We have modeled the transformation of cellulose I beta to a high temperature (550 K) structure, which is considered to be the first step in cellulose pyrolysis. We have performed molecular dynamics simulations at constant pressure using the GROMOS 45a4 united atom forcefield. To test the forcefield, we computed the density, thermal expansion coefficient, total dipole moment, and dielectric constant of cellulose I beta, finding broad agreement with experimental results. We computed infrared (IR) spectra of cellulose I beta over the range 300-550 K as a probe of hydrogen bonding. Computed IR spectra were found to agree semi-quantitatively with experiment, especially in the O-H stretching region. We assigned O-H stretches using a novel synthesis of normal mode analysis and power spectrum methods. Simulated IR spectra at elevated temperatures suggest a structural transformation above 450 K, a result in agreement with experimental IR results. The low-temperature (300-400 K) structure of cellulose I beta is dominated by intrachain hydrogen bonds, whereas in the high-temperature structure (450-550 K), many of these transform to longer, weaker interchain hydrogen bonds. A three-dimensional hydrogen bonding network emerges at high temperatures due to formation of new interchain hydrogen bonds, which may explain the stability of the cellulose structure at such high temperatures. (C) 2011 American Institute of Physics. [doi:10.1063/1.3646306]
引用
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页数:13
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