自然电子轨道NBO分析方法.doc

自然键轨道(NBO)分析方法 分子轨道未经定域化处理，将导致计算结果与我们通常的成键概念有所不同。例如在乙烯分子中，碳碳之间为双键，但在正则MO中，反映C与C之间成键作用的MO可能有多个，因此根据正则MO的结果，我们无法断定CC是单键还是双键。此时，通过对正则MO的定域化处理，可以得到通常意义上的成键图像。正则MO的定域化处理方法较多，其中较为常用的是NBO方法，其使用方法是在输入文件中添加关键词：POP=NBO以乙烯分子为例：%mem=32mb#p b3lyp/3-21g pop=nbo 进行NBO成键分析The NBO analysis of ethylene0,1CC,1,CCH,1,CH,2,HCCH,1,CH,2,HCC,3,180.,0H,2,CH,1,HCC,3,180.,0H,2,CH,1,HCC,4,180.,0CC=1.31477CH=1.07363HCC=121.8867 Entering Link 1 = C:G03Wl1.exe PID= 2100. Copyright (c) 1988,1990,1992,1993,1995,1998,2003, Gaussian, Inc. All Rights Reserved. This is the Gaussian(R) 03 program. It is based on the the Gaussian(R) 98 system (copyright 1998, Gaussian, Inc.), the Gaussian(R) 94 system (copyright 1995, Gaussian, Inc.), the Gaussian 92(TM) system (copyright 1992, Gaussian, Inc.), the Gaussian 90(TM) system (copyright 1990, Gaussian, Inc.), the Gaussian 88(TM) system (copyright 1988, Gaussian, Inc.), the Gaussian 86(TM) system (copyright 1986, Carnegie Mellon University), and the Gaussian 82(TM) system (copyright 1983, Carnegie Mellon University). Gaussian is a federally registered trademark of Gaussian, Inc. This software contains proprietary and confidential information, including trade secrets, belonging to Gaussian, Inc. This software is provided under written license and may be used, copied, transmitted, or stored only in accord with that written license. The following legend is applicable only to US Government contracts under DFARS: RESTRICTED RIGHTS LEGEND Use, duplication or disclosure by the US Government is subject to restrictions as set forth in subparagraph (c)(1)(ii) of the Rights in Technical Data and Computer Software clause at DFARS 252.227-7013. Gaussian, Inc. Carnegie Office Park, Building 6, Pittsburgh, PA 15106 USA The following legend is applicable only to US Government contracts under FAR: RESTRICTED RIGHTS LEGEND Use, reproduction and disclosure by the US Government is subject to restrictions as set forth in subparagraph (c) of the Commercial Computer Software - Restricted Rights clause at FAR 52.227-19. Gaussian, Inc. Carnegie Office Park, Building 6, Pittsburgh, PA 15106 USA - Warning - This program may not be used in any manner that competes with the business of Gaussian, Inc. or will provide assistance to any competitor of Gaussian, Inc. The licensee of this program is prohibited from giving any competitor of Gaussian, Inc. access to this program. By using this program, the user acknowledges that Gaussian, Inc. is engaged in the business of creating and licensing software in the field of computational chemistry and represents and warrants to the licensee that it is not a competitor of Gaussian, Inc. and that it will not use this program in any manner prohibited above. - Cite this work as: Gaussian 03, Revision B.01, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, J. A. Montgomery, Jr., T. Vreven, K. N. Kudin, J. C. Burant, J. M. Millam, S. S. Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G. Scalmani, N. Rega, G. A. Petersson, H. Nakatsuji, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J. E. Knox, H. P. Hratchian, J. B. Cross, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, P. Y. Ayala, K. Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg, V. G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain, O. Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. V. Ortiz, Q. Cui, A. G. Baboul, S. Clifford, J. Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz, I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, W. Chen, M. W. Wong, C. Gonzalez, and J. A. Pople, Gaussian, Inc., Pittsburgh PA, 2003. * Gaussian 03: x86-Win32-G03RevB.01 3-Mar-2003 22-Dec-2014 * %mem=32mb Default route: MaxDisk=2000MB - #p b3lyp/3-21G pop=NBO - 1/38=1/1; 2/17=6,18=5,40=1/2; 3/5=5,11=2,16=1,25=1,30=1,74=-5/1,2,3; 4/1; 5/5=2,32=1,38=5/2; 6/7=2,8=2,9=2,10=2,28=1/1,7; 99/5=1,9=1/99; Leave Link 1 at Mon Dec 22 10:12:15 2014, MaxMem= 4194304 cpu: 0.0 (Enter C:G03Wl101.exe) - The NBO analysis of ethylene - Symbolic Z-matrix: Charge = 0 Multiplicity = 1 C C 1 CC H 1 CH 2 HCC H 1 CH 2 HCC 3 180. 0 H 2 CH 1 HCC 3 180. 0 H 2 CH 1 HCC 4 180. 0 Variables: CC 1.31477 CH 1.07363 HCC 121.8867 Isotopes and Nuclear Properties: Atom 1 2 3 4 5 6 IAtWgt= 12 12 1 1 1 1 AtmWgt= 12.0000000 12.0000000 1.0078250 1.0078250 1.0078250 1.0078250 IAtSpn= 0 0 1 1 1 1 AtZEff= 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 AtQMom= 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 0.0000000 AtGFac= 0.0000000 0.0000000 2.7928460 2.7928460 2.7928460 2.7928460 Leave Link 101 at Mon Dec 22 10:12:15 2014, MaxMem= 4194304 cpu: 0.0 (Enter C:G03Wl202.exe) Input orientation: - Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z - 1 6 0 0.000000 0.000000 0.000000 2 6 0 0.000000 0.000000 1.314770 3 1 0 0.911613 0.000000 -0.567136 4 1 0 -0.911613 0.000000 -0.567136 5 1 0 -0.911613 0.000000 1.881906 6 1 0 0.911613 0.000000 1.881906 - Distance matrix (angstroms): 1 2 3 4 5 1 C 0.000000 2 C 1.314770 0.000000 3 H 1.073630 2.091078 0.000000 4 H 1.073630 2.091078 1.823226 0.000000 5 H 2.091078 1.073630 3.053188 2.449041 0.000000 6 H 2.091078 1.073630 2.449041 3.053188 1.823226 6 6 H 0.000000 Stoichiometry C2H4 Framework group D2HC2(C.C),SG(H4) Deg. of freedom 3 Full point group D2H NOp 8 Largest Abelian subgroup D2H NOp 8 Largest concise Abelian subgroup D2 NOp 4 Standard orientation: - Center Atomic Atomic Coordinates (Angstroms) Number Number Type X Y Z - 1 6 0 0.000000 0.000000 0.657385 2 6 0 0.000000 0.000000 -0.657385 3 1 0 0.000000 0.911613 1.224521 4 1 0 0.000000 -0.911613 1.224521 5 1 0 0.000000 -0.911613 -1.224521 6 1 0 0.000000 0.911613 -1.224521 - Rotational constants (GHZ): 150.8519412 30.7849006 25.5672912 Leave Link 202 at Mon Dec 22 10:12:15 2014, MaxMem= 4194304 cpu: 0.0 (Enter C:G03Wl301.exe) Standard basis: 3-21G (6D, 7F) There are 7 symmetry adapted basis functions of AG symmetry. There are 0 symmetry adapted basis functions of B1G symmetry. There are 2 symmetry adapted basis functions of B2G symmetry. There are 4 symmetry adapted basis functions of B3G symmetry. There are 0 symmetry adapted basis functions of AU symmetry. There are 7 symmetry adapted basis functions of B1U symmetry. There are 4 symmetry adapted basis functions of B2U symmetry. There are 2 symmetry adapted basis functions of B3U symmetry. Integral buffers will be 262144 words long. Raffenetti 2 integral format. Two-electron integral symmetry is turned on. 26 basis functions, 42 primitive gaussians, 26 cartesian basis functions 8 alpha electrons 8 beta electrons nuclear repulsion energy 33.7515964359 Hartrees. IExCor= 402 DFT=T Ex=B+HF Corr=LYP ExCW=0 ScaHFX= 0.200000 ScaDFX= 0.800000 0.720000 1.000000 0.810000 IRadAn= 0 IRanWt= -1 IRanGd= 0 ICorTp=0 NAtoms= 6 NActive= 6 NUniq= 2 SFac= 5.66D+00 NAtFMM= 60 Big=F Leave Link 301 at Mon Dec 22 10:12:16 2014, MaxMem= 4194304 cpu: 0.0 (Enter C:G03Wl302.exe) NPDir=0 NMtPBC= 1 NCelOv= 1 NCel= 1 NClECP= 1 NCelD= 1 NCelK= 1 NCelE2= 1 NClLst= 1 CellRange= 0.0. One-electron integrals computed using PRISM. One-electron integral symmetry used in STVInt NBasis= 26 RedAO= T NBF= 7 0 2 4 0 7 4 2 NBsUse= 26 1.00D-06 NBFU= 7 0 2 4 0 7 4 2 Precomputing XC quadrature grid using IXCGrd= 2 IRadAn= 0 IRanWt= -1 IRanGd= 0. NRdTot= 359 NPtTot= 45406 NUsed= 47035 NTot= 47051 NSgBfM= 26 26 26 26. Leave Link 302 at Mon Dec 22 10:12:16 2014, MaxMem= 4194304 cpu: 0.0 (Enter C:G03Wl303.exe) DipDrv: MaxL=1. Leave Link 303 at Mon Dec 22 10:12:16 2014, MaxMem= 4194304 cpu: 0.0 (Enter C:G03Wl401.exe) Harris functional with IExCor= 402 diagonalized for initial guess. ExpMin= 1.83D-01 ExpMax= 1.72D+02 ExpMxC= 1.72D+02 IAcc=1 IRadAn= 1 AccDes= 1.00D-06 HarFok: IExCor= 402 AccDes= 1.00D-06 IRadAn= 1 IDoV=1 ScaDFX= 1.000000 1.000000 1.000000 1.000000 Harris En= -78.2050951851189 Initial guess orbital symmetries: Occupied (B1U) (AG) (AG) (B1U) (B2U) (AG) (B3G) (B3U) Virtual (B2G) (B2U) (AG) (B1U) (B3G) (B1U) (AG) (B3U) (B2U) (B2G) (B1U) (AG) (B3G) (B2U) (B1U) (AG) (B3G) (B1U) The electronic state of the initial guess is 1-AG. Leave Link 401 at Mon Dec 22 10:12:16 2014, MaxMem= 4194304 cpu: 0.0 (Enter C:G03Wl502.exe) Warning! Cutoffs for single-point calculations used. Closed shell SCF: Requested convergence on RMS density matrix=1.00D-04 within 128 cycles. Requested convergence on MAX density matrix=1.00D-02. Requested convergence on energy=5.00D-05. No special actions if energy rises. Using DIIS extrapolation, IDIIS= 1040. Integral symmetry usage will be decided dynamically. 47034 words used for storage of precomputed grid. Keep R1 integrals in memory in canonical form, NReq= 537976. IEnd= 66709 IEndB= 66709 NGot= 4194304 MDV= 4083148 LenX= 4083148 Symmetry not used in FoFDir. MinBra= 0 MaxBra= 1 Meth= 1. IRaf= 0 NMat= 1 IRICut= 1 DoRegI=T DoRafI=F ISym2E= 0 JSym2E=0. Cycle 1 Pass 1 IDiag 1: E= -78.0698393698835 DIIS: error= 6.31D-02 at cycle 1 NSaved= 1. NSaved= 1 IEnMin= 1 EnMin= -78.0698393698835 IErMin= 1 ErrMin= 6.31D-02 ErrMax= 6.31D-02 EMaxC= 1.00D-01 BMatC= 8.34D-02 BMatP= 8.34D-02 IDIUse=3 WtCom= 3.69D-01 WtEn= 6.31D-01 Coeff-Com: 0.100D+01 Coeff-En: 0.100D+01 Coeff: 0.100D+01 Gap= 0.296 Goal= None Shift= 0.000 GapD= 0.296 DampG=1.000 DampE=0.500 DampFc=0.5000 IDamp=-1. Damping current iteration by 5.00D-01 RMSDP=2.19D-02 MaxDP=1.08D-01 OVMax= 1.56D-01 Cycle 2 Pass 1 IDiag 1: E= -78.1160719860205 Delta-E= -0.046232616137 Rises=F Damp=T DIIS: error= 6.35D-03 at cycle 2 NSaved= 2. NSaved= 2 IEnMin= 2 EnMin= -78.1160719860205 IErMin= 2 ErrMin= 6.35D-03 ErrMax= 6.35D-03 EMaxC= 1.00D-01 BMatC= 1.02D-03 BMatP= 8.34D-02 IDIUse=3 WtCom= 9.37D-01 WtEn= 6.35D-02 Coeff-Com: -0.313D-01 0.103D+01 Coeff-En: 0.000D+00 0.100D+01 Coeff: -0.293D-01 0.103D+01 Gap= 0.301 Goal= None Shift= 0.000 RMSDP=1.90D-03 MaxDP=8.30D-03 DE=-4.62D-02 OVMax= 7.45D-02 Cycle 3 Pass 1 IDiag 1: E= -78.1603678598281 Delta-E= -0.044295873808 Rises=F Damp=F DIIS: error= 6.21D-04 at cycle 3 NSaved= 3. NSaved= 3 IEnMin= 3 EnMin= -78.1603678598281 IErMin= 3 ErrMin= 6.21D-04 ErrMax= 6.21D-04 EMaxC= 1.00D-01 BMatC= 6.84D-06 BMatP= 1.02D-03 IDIUse=3 WtCom= 9.94D-01 WtEn= 6.21D-03 Coeff-Com: -0.592D-02 0.384D-01 0.967D+00 Coeff-En: 0.000D+00 0.000D+00 0.100D+01 Coeff: -0.588D-02 0.382D-01 0.968D+00 Gap= 0.299 Goal= None Shift= 0.000 RMSDP=2.06D-04 MaxDP=2.07D-03 DE=-4.43D-02 OVMax= 1.38D-03 Cycle 4 Pass 1 IDiag 1: E= -78.1603763313634 Delta-E= -0.000008471535 Rises=F Damp=F DIIS: error= 6.41D-05 at cycle 4 NSaved= 4. NSaved= 4 IEnMin= 4 EnMin= -78.1603763313634 IErMin= 4 ErrMin= 6.41D-05 ErrMax= 6.41D-05 EMaxC= 1.00D-01 BMatC= 7.72D-08 BMatP= 6.84D-06 IDIUse=1 WtCom= 1.00D+00 WtEn= 0.00D+00 Coeff-Com: 0.287D-03-0.320D-02 0.637D-01 0.939D+00 Coeff: 0.287D-03-0.320D-02 0.637D-01 0.939D+00 Gap= 0.299 Goal= None Shift= 0.000 RMSDP=2.36D-05 MaxDP=2.31D-04 DE=-8.47D-06 OVMax= 1.12D-04 SCF Done: E(RB+HF-LYP) = -78.1603763314 A.U. after 4 cycles Convg = 0.2365D-04 -V/T = 2.0085 S*2 = 0.0000 KE= 7.750227529344D+01 PE=-2.479757014870D+02 EE= 5.856145342636D+01 Leave Link 502 at Mon Dec 22 10:12:16 2014, MaxMem= 4194304 cpu: 0.0 (Enter C:G03Wl601.exe) Copying SCF densities to generalized density rwf, ISCF=0 IROHF=0. * Population analysis using the SCF density. * Orbital symmetries: Occupied (B1U) (AG) (AG) (B1U) (B2U) (AG) (B3G) (B3U) Virtual (B2G) (AG) (B2U) (B1U) (B3G) (B1U) (AG) (B2U) (B3U) (B2G) (B1U) (AG) (B3G) (B2U) (B1U) (B3G) (AG) (B1U) The electronic state is 1-AG. Alpha occ. eigenvalues - -10.11473 -10.11384 -0.76450 -0.57896 -0.47393 Alpha occ. eigenvalues - -0.42587 -0.35294 -0.27287 Alpha virt. eigenvalues - 0.02574 0.14839 0.15900 0.18609 0.27999 Alpha virt. eigenvalues - 0.37431 0.65808 0.70943 0.72999 0.80352 Alpha virt. eigenvalues - 0.84423 0.87627 1.02327 1.06600 1.10465 Alpha virt. eigenvalues - 1.38482 1.40489 1.71336 Condensed to atoms (all electrons): 1 2 3 4 5 6 1 C 5.133974 0.569404 0.383966 0.383966 -0.048019 -0.048019 2 C 0.569404 5.133974 -0.048019 -0.048019 0.383966 0.383966 3 H 0.383966 -0.048019 0.510104 -0.031643 0.003521 -0.005564 4 H 0.383966 -0.048019 -0.031643 0.510104 -0.005564 0.003521 5 H -0.048019 0.383966 0.003521 -0.005564 0.510104 -0.031643 6 H -0.048019 0.383966 -0.005564 0.003521 -0.031643 0.510104 Mulliken atomic charges: 1 1 C -0.375272 2 C -0.375272 3 H 0.187636 4 H 0.187636 5 H 0.187636 6 H 0.187636 Sum of Mulliken charges= 0.00000 Atomic charges with hydrogens summed into heavy atoms: 1 1 C 0.000000 2 C 0.000000 3 H 0.000000 4 H 0.000000 5 H 0.000000 6 H 0.000000 Sum of Mulliken charges= 0.00000 Electronic spatial extent (au): = 81.0319 Charge= 0.0000 electrons Dipole moment (field-independent basis, Debye): X= 0.0000 Y= 0.0000 Z= 0.0000 Tot= 0.0000 Quadrupole moment (field-independent basis, Debye-Ang): XX= -15.1825 YY= -12.1400 ZZ= -11.9841 XY= 0.0000 XZ= 0.0000 YZ= 0.0000 Traceless Quadrupole moment (field-independent basis, Debye-Ang): XX= -2.0803 YY= 0.9622 ZZ= 1.1181 XY= 0.0000 XZ= 0.0000 YZ= 0.0000 Octapole moment (field-independent basis, Debye-Ang*2): XXX= 0.0000 YYY= 0.0000 ZZZ= 0.0000 XYY= 0.0000 XXY= 0.0000 XXZ= 0.0000 XZZ= 0.0000 YZZ= 0.0000 YYZ= 0.0000 XYZ= 0.0000 Hexadecapole moment (field-independent basis, Debye-Ang*3): XXXX= -15.4496 YYYY= -24.7454 ZZZZ= -63.7369 XXXY= 0.0000 XXXZ= 0.0000 YYYX= 0.0000 YYYZ= 0.0000 ZZZX= 0.0000 ZZZY= 0.0000 XXYY= -7.2693 XXZZ= -14.2187 YYZZ= -12.4223 XXYZ= 0.0000 YYXZ= 0.0000 ZZXY= 0.0000 N-N= 3.375159643587D+01 E-N=-2.479768211140D+02 KE= 7.750227529344D+01 Symmetry AG KE= 3.728364031898D+01 Symmetry B1G KE= 0.000000000000D+00 Symmetry B2G KE= 4.245017828591D-33 Symmetry B3G KE= 2.103943491718D+00 Symmetry AU KE= 0.000000000000D+00 Symmetry B1U KE= 3.412949996315D+01 Symmetry B2U KE= 1.892312781415D+00 Symmetry B3U KE= 2.092878738177D+00 No NMR shielding tensors so no spin-rotation constants. Leave Link 601 at Mon Dec 22 10:12:16 2014, MaxMem= 4194304 cpu: 0.0 (Enter C:G03Wl607.exe) *Gaussian NBO Version 3.1* N A T U R A L A T O M I C O R B I T A L A N D N A T U R A L B O N D O R B I T A L A N A L Y S I S *Gaussian NBO Version 3.1* /RESON / : Allow strongly delocalized NBO set Analyzing the SCF density Job title: The NBO analysis of ethylene Storage needed: 2186 in NPA, 2827 in NBO ( 4194170 available) NATURAL POPULATIONS: Natural atomic orbital occupancies NAO Atom No lang Type(AO) Occupancy Energy - 1 C 1 S Cor( 1S) 1.99851 -9.96032 2 C 1 S Val( 2S) 1.04384 -0.20539 3 C 1 S Ryd( 3S) 0.00118 1.46031 4 C 1 px Val( 2p) 0.99869 -0.10983 5 C 1 px Ryd( 3p) 0.00131 0.75302 6 C 1 py Val( 2p) 1.21847 -0.03809 7 C 1 py Ryd( 3p) 0.00302 1.0464