A comparison between entropies of aromatic compounds from quantum mechanical calculations and experiment

被引:9
作者
Kassaee, Mohamad H.
Keffer, David J. [1 ]
Steele, William V.
机构
[1] Univ Tennessee, Dept Chem Engn, Knoxville, TN 37996 USA
[2] Oak Ridge Natl Lab, Nucl Sci & Technol Div, Oak Ridge, TN 37831 USA
来源
JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM | 2007年 / 802卷 / 1-3期
关键词
ab initio; quantum mechanical computation; DFT; entropy; vibrational frequencies; benzene; toluene; xylene;
D O I
10.1016/j.theochem.2006.09.007
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
In this work, we perform a set of quantum mechanical and statistical mechanical calculations to generate the entropy of five simple, aromatic compounds-benzene, toluene, p-xylene, m-xylene and o-xylene-in the ideal gas state. We systematically examine how the choice of quantum mechanical level of theory and size of basis set impact the agreement between theory and experiment. Regardless of level of theory and basis set, all calculations require an empirical scaling factor to correct the vibrational contribution to the entropy. Once this scaling factor is applied, there is at most nominal advantage in more sophisticated levels of theory or increased basis set size, while a heavy computational penalty is paid for the more advanced theory. We find that the variation in scaling factor across these aromatic compounds is on average 0.3%. Across a range from 250 to 540 K, the difference in the entropies obtained from all quantum mechanical calculations and from experiment is less than half a percent. (c) 2006 Elsevier B.V. All rights reserved.
引用
收藏
页码:23 / 34
页数:12
相关论文
共 25 条
  • [11] Peptide Bond Distortions from Planarity: New Insights from Quantum Mechanical Calculations and Peptide/Protein Crystal Structures
    Improta, Roberto
    Vitagliano, Luigi
    Esposito, Luciana
    PLOS ONE, 2011, 6 (09):
  • [12] Evidence for a strong selenium-aromatic interaction derived from crystallographic data and ab initio quantum chemical calculations
    Hartman, Izabela
    Raia, Carlo A.
    Zauhar, Randy J.
    BIOPOLYMERS, 2006, 83 (06) : 595 - 613
  • [13] Experimental and Quantum Mechanical Study of Nucleophilic Substitution Reactions of meta- and para-Substituted Benzyl Bromides with Benzylamine in Methanol: Synergy Between Experiment and Theory
    Sanjeev, Rachuru
    Ravi, Ramavath
    Jagannadham, Vandanapu
    Skelton, Adam A.
    AUSTRALIAN JOURNAL OF CHEMISTRY, 2017, 70 (01) : 90 - 100
  • [14] Mechanisms of the gas-phase decomposition of C-nitro compounds inferred from quantum chemical calculations
    Khrapkovskii, G. M.
    Shamov, A. G.
    Nikolaeva, E. V.
    Chachkov, D. V.
    RUSSIAN CHEMICAL REVIEWS, 2009, 78 (10) : 903 - 943
  • [15] IDEAL-GAS PROPERTIES OF NEW REFRIGERANTS FROM QUANTUM-MECHANICAL AB-INITIO CALCULATIONS
    LUCAS, K
    DELFS, U
    BUSS, V
    SPEIS, M
    INTERNATIONAL JOURNAL OF THERMOPHYSICS, 1993, 14 (05) : 993 - 1006
  • [16] Substituent effect on the interaction of aromatic primary amines and diamines with supercritical CO2 from infrared spectroscopy and quantum calculations
    Farbos, Baptiste
    Tassaing, Thierry
    PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 2009, 11 (25) : 5052 - 5061
  • [17] Study on the interaction between dinaphthosulfide-substituted macrocyclic diamides and some metal ions: experimental measurements vs. quantum mechanical calculations
    Mehdi Taghdiri
    Reza Behjatmanesh-Ardakani
    Abbas Shockravi
    Fatemeh Taheri
    Hanif Fattahi
    Journal of Inclusion Phenomena and Macrocyclic Chemistry, 2012, 73 : 255 - 262
  • [18] Study on the interaction between dinaphthosulfide-substituted macrocyclic diamides and some metal ions: experimental measurements vs. quantum mechanical calculations
    Taghdiri, Mehdi
    Behjatmanesh-Ardakani, Reza
    Shockravi, Abbas
    Taheri, Fatemeh
    Fattahi, Hanif
    JOURNAL OF INCLUSION PHENOMENA AND MACROCYCLIC CHEMISTRY, 2012, 73 (1-4) : 255 - 262
  • [19] Clustering Analysis, Structure Fingerprint Analysis, and Quantum Chemical Calculations of Compounds from Essential Oils of Sunflower (Helianthus annuus L.) Receptacles
    He, Yi
    Liu, Kaifeng
    Han, Lu
    Han, Weiwei
    INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES, 2022, 23 (17)
  • [20] Conformational landscape of small organosilicon compounds from the combined use of gas electron diffraction, IR and Raman spectroscopies and quantum chemical calculations: diethyldichlorosilane
    Montejo, Manuel
    Wann, Derek A.
    Rodriguez Ortega, Pilar G.
    Robertson, Heather E.
    Marquez, Fernando
    Rankin, David W. H.
    Lopez Gonzalez, Juan Jesus
    JOURNAL OF RAMAN SPECTROSCOPY, 2010, 41 (10) : 1323 - 1330