化工学报
化工學報
화공학보
JOURNAL OF CHEMICAL INDUSY AND ENGINEERING (CHINA)
2015年
5期
1627-1632
,共6页
丁烯醛%Gibbs系综Monte Carlo%相平衡%力场%计算机模拟%统计热力学
丁烯醛%Gibbs繫綜Monte Carlo%相平衡%力場%計算機模擬%統計熱力學
정희철%Gibbs계종Monte Carlo%상평형%력장%계산궤모의%통계열역학
crotonaldehyde%Gibbs ensemble Monte Carlo%phase equilibria%force field%computer simulation%statistical thermodynamics
采用Gibbs系综Monte Carlo方法，对TraPPE-UA力场中缺失的烯醛类力场参数进行了补充和验证，为模拟含烯醛体系汽液相平衡奠定基础。分别使用B3LYP 6-311G (d, p)和MP26-31G (d, p)方法计算了丁烯醛分子中缺失的键参数、二面角扭转项参数。采用构建的丁烯醛分子的 TraPPE-UA 力场参数,分别计算了丁烯醛纯组分、丁烯醛与乙醛二元体系的汽液相平衡数据，并将模拟结果与实验值进行比较。丁烯醛纯物质模拟结果与实验数据相比液相密度偏差为0.28%～1.23%，模拟结果表明构建的TraPPE-UA力场对丁烯醛分子具有较高的模拟精度。丁烯醛与乙醛二元体系的模拟结果与实验数据相比最小误差为0.13%，但随着温度上升有增大趋势，最大误差为7.44%。
採用Gibbs繫綜Monte Carlo方法，對TraPPE-UA力場中缺失的烯醛類力場參數進行瞭補充和驗證，為模擬含烯醛體繫汽液相平衡奠定基礎。分彆使用B3LYP 6-311G (d, p)和MP26-31G (d, p)方法計算瞭丁烯醛分子中缺失的鍵參數、二麵角扭轉項參數。採用構建的丁烯醛分子的 TraPPE-UA 力場參數,分彆計算瞭丁烯醛純組分、丁烯醛與乙醛二元體繫的汽液相平衡數據，併將模擬結果與實驗值進行比較。丁烯醛純物質模擬結果與實驗數據相比液相密度偏差為0.28%～1.23%，模擬結果錶明構建的TraPPE-UA力場對丁烯醛分子具有較高的模擬精度。丁烯醛與乙醛二元體繫的模擬結果與實驗數據相比最小誤差為0.13%，但隨著溫度上升有增大趨勢，最大誤差為7.44%。
채용Gibbs계종Monte Carlo방법，대TraPPE-UA력장중결실적희철류력장삼수진행료보충화험증，위모의함희철체계기액상평형전정기출。분별사용B3LYP 6-311G (d, p)화MP26-31G (d, p)방법계산료정희철분자중결실적건삼수、이면각뉴전항삼수。채용구건적정희철분자적 TraPPE-UA 력장삼수,분별계산료정희철순조분、정희철여을철이원체계적기액상평형수거，병장모의결과여실험치진행비교。정희철순물질모의결과여실험수거상비액상밀도편차위0.28%～1.23%，모의결과표명구건적TraPPE-UA력장대정희철분자구유교고적모의정도。정희철여을철이원체계적모의결과여실험수거상비최소오차위0.13%，단수착온도상승유증대추세，최대오차위7.44%。
Gibbs ensemble Monte Carlo method with TraPPE-UA force field was used to study the vapor-liquid phase equilibrium of systems containing crotonaldehyde. To lay the foundation for the vapor-liquid phase equilibrium simulation, quantum chemistry calculations with B3LYP 6-311G (d, p) and MP2 6-31G (d, p) basis sets were firstly performed to obtain the lacking bond parameters and torsional parameters for crotonaldehyde molecular. Based on these parameters, a new TraPPE-UA force field was developed. Vapor-liquid phase equilibrium data of pure crotonaldehyde and its mixture with ethanal were calculated using the new force field and compared with experiment data. The saturated liquid densities of pure crotonaldehyde predicted by the new force field were in close agreement with experimental results, with deviations from 0.28% to 1.23%. This demonstrated that the new TraPPE-UA force field manifested high simulation precision for crotonaldehyde. For the binary system consisting of crotonaldehyde and ethanal, the deviation between simulations and experiments increased with rising temperature, and the minimum and maximum values were 0.13% and 7.44%, respectively.
