The density functional theory （DFT） is the most popular method for evaluating bond dis- sociation enthalpies （BDEs） of most molecules. Thus, we are committed to looking for alternative methods that can balance the...The density functional theory （DFT） is the most popular method for evaluating bond dis- sociation enthalpies （BDEs） of most molecules. Thus, we are committed to looking for alternative methods that can balance the computational cost and higher precision to the best for large systems. The performance of DFT, double-hybrid DFT, and high-level com- posite methods are examined. The tested sets contain monocyclic and polycyclic aromatic molecules, branched hydrocarbons, small inorganic molecules, etc. The results show that the mPW2PLYP and G4MP2 methods achieve reasonable agreement with the benchmark val- ues for most tested molecules, and the mean absolute deviations are 2.43 and 1.96 kcal/mol after excluding the BDEs of branched hydrocarbons. We recommend the G4MP2 is the most appropriate method for small systems （atoms number≤20）; the double-hybrid DFT methods are advised for large aromatic molecules in medium size （20≤atoms number≤50）, and the double-hybrid DFT methods with empirical dispersion correction are recommended for long-chain and branched hydrocarbons in the same size scope; the DFT methods are ad- vised to apply for large systems （atoms number〉50）, and the M06-2X and B3P86 methods are also favorable. Moreover, the differences of optimized geometry of different methods are discussed and the effects of basis sets for various methods are investigated.展开更多
The altimeter normalized radar cross section(NRCS) has been used to retrieve the sea surface wind speed for decades, and more than a dozen of wind speed retrieval algorithms have been proposed. Despite the continuing ...The altimeter normalized radar cross section(NRCS) has been used to retrieve the sea surface wind speed for decades, and more than a dozen of wind speed retrieval algorithms have been proposed. Despite the continuing efforts to improve the wind speed measurements, a bias dependence on wave state persists in all wind algorithms. On the basis of recent evidence that short waves are essentially modulated by local winds and much less affected by wave state, we proposed a physics-based approach to retrieve the wind speed from the dual-frequency difference in terms of the mean square slope of short waves. A collocated dataset of coincident altimeter/buoy measurements were used to develop and validate the approach. Validation against buoy measurements indicates that the approach is almost unbiased and has an overall root mean square error of 1.24 m s-1, which is 5.3% lower than the single-parameter algorithm in operational use(Witter and Chelton, 1991) and 2.4% lower than another dual-frequency approach(Chen et al., 2002). Furthermore, the results indicate that the new approach significantly improves the wave-dependent bias compared to the single-parameter algorithm. The capacity of altimeter to retrieve sea surface wind speed appears to be limited for the case of winds below 3 m s-1. The validity of the approach at high winds needs to be further examined in the future study.展开更多
文摘The density functional theory （DFT） is the most popular method for evaluating bond dis- sociation enthalpies （BDEs） of most molecules. Thus, we are committed to looking for alternative methods that can balance the computational cost and higher precision to the best for large systems. The performance of DFT, double-hybrid DFT, and high-level com- posite methods are examined. The tested sets contain monocyclic and polycyclic aromatic molecules, branched hydrocarbons, small inorganic molecules, etc. The results show that the mPW2PLYP and G4MP2 methods achieve reasonable agreement with the benchmark val- ues for most tested molecules, and the mean absolute deviations are 2.43 and 1.96 kcal/mol after excluding the BDEs of branched hydrocarbons. We recommend the G4MP2 is the most appropriate method for small systems （atoms number≤20）; the double-hybrid DFT methods are advised for large aromatic molecules in medium size （20≤atoms number≤50）, and the double-hybrid DFT methods with empirical dispersion correction are recommended for long-chain and branched hydrocarbons in the same size scope; the DFT methods are ad- vised to apply for large systems （atoms number〉50）, and the M06-2X and B3P86 methods are also favorable. Moreover, the differences of optimized geometry of different methods are discussed and the effects of basis sets for various methods are investigated.
基金supported by the National High Technology Research and Development Program of China (2013 AA09A505)
文摘The altimeter normalized radar cross section(NRCS) has been used to retrieve the sea surface wind speed for decades, and more than a dozen of wind speed retrieval algorithms have been proposed. Despite the continuing efforts to improve the wind speed measurements, a bias dependence on wave state persists in all wind algorithms. On the basis of recent evidence that short waves are essentially modulated by local winds and much less affected by wave state, we proposed a physics-based approach to retrieve the wind speed from the dual-frequency difference in terms of the mean square slope of short waves. A collocated dataset of coincident altimeter/buoy measurements were used to develop and validate the approach. Validation against buoy measurements indicates that the approach is almost unbiased and has an overall root mean square error of 1.24 m s-1, which is 5.3% lower than the single-parameter algorithm in operational use(Witter and Chelton, 1991) and 2.4% lower than another dual-frequency approach(Chen et al., 2002). Furthermore, the results indicate that the new approach significantly improves the wave-dependent bias compared to the single-parameter algorithm. The capacity of altimeter to retrieve sea surface wind speed appears to be limited for the case of winds below 3 m s-1. The validity of the approach at high winds needs to be further examined in the future study.
