回H厄与 What Theory Can Do Strength and Weakness
What Theory Can Do Strength and Weakness
Center for Theoretical Chemical Physics Laboratory of Molecular Catalysis mnovative Material 理论计算起到了非常重要的作用 EQUILIBRIUM KINETIC MEASUREMENTS MEASUREMENTS THERMOCHEMICAL KINETICS MECHANISM QUANTUM CHEMICAL CALCULATIONS VALENCY THEORY Fig.1 The linkages between thermochemical kinetics and other subjects Ref.Walsh.R.Chem.Soc.Rev.2008.37.686. 振华制 2013/10/14 What Theory Can Do 造
李 振 华 制 2013/10/14 What Theory Can Do 2 造 理论计算起到了非常重要的作用 Fig. 1 The linkages between thermochemical kinetics and other subjects. Ref. Walsh, R. Chem. Soc. Rev. 2008, 37, 686
Center for Theoretical Chemical Physics Laboratory of Molecular Catalysis mnovative Material Strength For small and regular molecules Chemical Accuracy: Energetics:Error 1 kcal/mol Structures:Error in Bond Lengths <0.01 A Frequencies:A few cm-l 李振华 2013/10/14 What Theory Can Do 3 造
李 振 华 制 2013/10/14 What Theory Can Do 3 造 Strength For small and regular molecules Chemical Accuracy: Energetics: Error < 1 kcal/mol Structures: Error in Bond Lengths < 0.01 Å Frequencies: A few cm-1
Center for Theoretical Chemical Physics Laboratory of Molecular Catalysis&Inovative Material Ref:Hoffman,B.C.;Sherrill,C.D.;Schaefer III,H.F.J.Chem.Phys.1997,107(24),10616 TABLE II.Theoretical harmonic vibrational frequencies (cm),IR inten- sities(km/mol,in parentheses),and zero-point vibrational energies(ZPVE, in kcal/mol)for H2S. 01 02 03 Method Symm.str. bend Asym.str. ZPVE DZP SCF 2863.40.6 1328.5(6.4) 2875.4(4.0) 10.10 DZP CISD 2807.1(3.2) 1260.8(7.6 2825.1(8.9) 9.85 DZP CISD[TQ]-B 2756.0 1237.6 2778.2 9.68 DZP CISD[TQ]-A 2761.7 1239.3 2786.6 9.70 DZP CISDTQ 2767.9(4.1) 1238.9(7.6) 2788.2(9.0) 9.71 TZ2P(f.d)SCF 2859.4(0.2) 1320.3(1.7) 2865.71.0) 10.07 TZ2P(f.d)CISD 2775.2(0.2) 1243.01.3) 2781.7(0.8) 9.72 TZ2P(f,d)CISD[TQ]-B 2716.9 1216.4 2728.6 9.52 TZ2P(f,d)CISD[TQ]-A 2720.4 1213.4 2730.7 9.53 TZ2P(f,d)CISDTQ 2721.5(0.4) 1214.01.1) 2729.31.1) 9.53 振华制 2013/10/14 What Theory Can Do 造
李 振 华 制 2013/10/14 What Theory Can Do 4 造 Ref: Hoffman, B.C.; Sherrill, C. D.; Schaefer III, H. F. J. Chem. Phys. 1997, 107(24), 10616
Center for Theoretical Chemical Physics Laboratory of Molecular Catalysis Innovative Material Ref:Bak K.L.et al.J.Chem.Phys.2001,114(15),6548 TABLE II.Equilibrium bond lengths Re in pm. CCSD(T)/ Molecule Bond Expt. Emp. Emp.-Expt. cc-pCVQZ H2 R 74.144 05 0 74.19 HF Rr 91.680(8 91.69 0.01 9158 H2O RoH 95.72 95.75 0.03 95.71 HOF R OH 96.57(16y 96.78 0.21 96.57 H2O2 RoH 96.71 000 卡0 96.19 HNC RNH 99.40(8 99.49 0.09 99.53 NHy RNN 101.1(6 101.16 0.06 101.12 N2H2 RNH 102.9(1)月 102.86 0.04 102.84 HNO RNH 44 105.17 t年+ 105.24 C2H2 RcH 106.215(17) 106.13 -0.09 106.21 HCN Rc 106.501(8y 106.53 0.03 106.55 C2H RcH 108.1(2y 108.07 0.03 108.09 CHa RcH 108.58(10 108.59 0.01 108.64 N2 RNN 109.768(5 109.77 0.00 109.81 CH2O Rcu 110.0520y 110.07 0.02 110.08 CH2 RcH 110.7(2) 110.63 0.07 110.68 CO Rco 112.832 112.84 0.01 112.89 HCN RcN 115.3242) 115.34 0.02 11538 C02 Rco 115.995m 116.01 0.01 116.04 HNC RcN 116.892) 116.87 -0.02 116.93 C2H2 Rcc 120.257(9P 120.37 0.11 120.37 CH2O Rco 120.33(10y 120.47 0.14 120.43 HNO RNO 年 120.86 g。 120.85 N2H2 RNN 124.71)9 124.57 -0.13 124.67 C2Ha Rcc 133.42y 133.07 -0.33 133.12 F2 RFF 141.193 141.24 0.05 141.13 HOF RFO 143.5031 143.44 -0.06 14326 H2O2 145.56 + 卡， 144.97 振华制 2013/10/14 Roo 5 造
李 振 华 制 2013/10/14 What Theory Can Do 5 造 Ref: Bak K. L. et al. J. Chem. Phys. 2001, 114(15), 6548