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C—C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 ethylene
0,1
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
CC=1.31477
CH=1.07363
HCC=121.8867
Entering Link 1 = C:\G03W\l1.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:\G03W\l101.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:\G03W\l202.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 D2H[C2"(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:\G03W\l301.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:\G03W\l302.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:\G03W\l303.exe)
DipDrv: MaxL=1.
Leave Link 303 at Mon Dec 22 10:12:16 2014, MaxMem= 4194304 cpu: 0.0
(Enter C:\G03W\l401.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:\G03W\l502.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
(Ente